Inorganic Chemistry Communications (v.20, #C)

Contents List (iii-xxii).

A novel 3d–4f heterometallic coordination polymer, namely, {[Sm2(PBDA)2·2H2O][Zn2(PBDA)2(Cl)2]}n (1), (H2PBDA = 3 -(pyridin-3-yl-oxy) benzene − 1,2-dicarboxylic acid) has been hydrothermally synthesized by using samarium(III) nitrate, H2PBDA acid and zinc chloride as raw materials, and characterized by elemental analysis, FT-IR, TG analysis and single crystal X-ray diffraction. Polymer 1 possesses two-dimensional (2D) network containing the original 1D heterometallic chain composed of [Sm2Zn2(PBDA)2] moieties. Variable temperature magnetic susceptibility studies reveal that 1 displays possible weak antiferromagnetic coupling between the neighboring Sm(III) ions, and the photoluminescent properties of polymer 1 as well as free H2PBDA ligand were also investigated.A novel 3d–4f heterometallic coordination polymer, {[Sm2(PBDA)2 ·2H2O] [Zn2(PBDA)2(Cl)2]}n has been hydrothermally synthesized by using samarium(III) nitrate. Complex 1 possesses two-dimensional (2D) network with the original 1D heterometallic chain composed of [Sm2Zn2(PBDA)2] moieties. Magnetic and the luminescent properties of compound 1 were also investigated.Display Omitted► A novel 3d–4f heterometallic coordination polymer, with 4, 4-connected network has been synthesized. ► To the best of our knowledge, complex 1 is the first (4, 4)-connected coordination framework containing nine-coordinated lanthanide as well as four-coordinated transition metal complex unit, so far. ► It displays possible weak antiferromagnetic coupling between the neighboring Sm(III) ions ► the luminescent properties of compound 1 were also investigated.
Keywords: Heterometallic coordination polymer; Flexible ligand; Luminescent property; Anti-magnetic properties;

Pyrazine bridged dinuclear lanthanide β-diketonate complexes of the type [(tfaa)3Ln(μ-pyz)Ln(tfaa)3] (tfaa is the anion of 1,1,1-trifluoro-2,4-pentanedione; pyz is pyrazine) were isolated by mixing [Ln(tfaa)3] and pyrazine in 2:1 molar ratio in chloroform. The elemental analysis, high yield and only one sharp resonance for the pyrazine moiety in the NMR spectrum are strong enough to support dinuclear complex formation. The oscillator strength of the hypersensitive 4G5/2, 2G7/2  ←  4I9/2 transition of the neodymium complex is approximately two fold higher than the mononuclear [Nd(tfaa)3H2O]. It confirms the presence of two neodymium ions both of which contribute to the oscillator strength. The red and green photoluminescence of Eu–Eu and Tb–Tb complexes, respectively, were scrutinized in solution and discussed.Pyrazine-bridged dinuclear complexes have been synthesized. One NMR resonance for pyrazine protons supports symmetric bridging of pyrazine to two [Ln(tfaa)3] units. The oscillator strenght of 4f-4f transitions of the dinuclear complex is twofold larger than the values for mononuclear complex. Eu and Tb complexes gives red and green luminescence, respectively.Display Omitted► Pyrazine-bridged Ln2 complexes of the type [(tfaa)3Ln]2(μ-pyz) are discussed. ► Only one NMR resonance due to pyrazine is observed. ► Red and green photoluminescence are observed from Eu and Tb complexes, respectively. ► The low molecular symmetry around Eu is inferred by stark splitting in the 5D0  →  7F1. ► 5D0  →  7F2/5D0  →  7F1 intensity ratio of [(tfaa)3|Eu(μ-pyz)Ln(tfaa)3] is about 10.89.
Keywords: Dinuclear lanthanide complexes; Pyrazine; 1,1,1-trifluoro-2,4-pentanedione; Hypersensitivity; Luminescence;

Synthesis, spectroscopic and photophysical properties of novel styryldiazepinoporphyrazine by Jaroslaw Piskorz; Ewa Tykarska; Maria Gdaniec; Tomasz Goslinski; Jadwiga Mielcarek (13-17).
A novel porphyrazine possessing two styryl substituents conjugated with each of four diazepine rings was synthesized and characterized using UV–vis, MS MALDI and various NMR techniques. Solvent effects on the electronic absorption spectra of this porphyrazine were determined in protic and aprotic solvents. The changes observed in the electronic absorption spectra seem to result mainly from solvation as there was no correlation between the coordinating strength of the solvent and the red shift. Also the potential photosensitizing activity of this novel porphyrazine was evaluated by measuring its ability to generate singlet oxygen, which was found to reach the yield (Φ Δ) of 0.11 in DMF.A novel porphyrazine possessing two styryl substituents conjugated with each of four diazepine rings was synthesized, characterized and subjected to photochemical studies. Potential photosensitizing activity of the novel porphyrazine was evaluated by measuring its ability to generate singlet oxygen, which was found to reach the yield of 0.11 in DMF.Display Omitted► New symmetrical styryldiazepinoporphyrazine was synthesized and characterized. ► Porphyrazine was subjected to spectroscopic studies including solvatochromic effects. ► Potential photosensitizing activity of novel porphyrazine was evaluated.
Keywords: Diazepine; Porphyrazine; Linstead macrocyclization; Solvatochromic effects; Singlet oxygen;

Two coordination polymers, {[Zn(Hpdcd)(bbi)](DMSO)(2H2O)]}n (1) and {[Ni(Hpdcd)(bbi)·H2O]2H2O}n (2) (H3pdcd = 1-(4-carboxyphenyl)-2,5-dimethyl, 1H-pyrrole-3,4-dicarboxylic acid, bbi = 1,1′-(1,4-butanediyl)bis(imidazole)), have been solvothermally synthesized. 1 shows a 1D isolated tube with a 1D→2D interdigital structure, while 2 exhibits a 2D deeply corrugated layer with a novel (2D→3D) interdigitated architecture.The metal ion is first connected by bbi ligand to form metallocycle or meso-helical chain as the subunits, which were further bridged by the partly deprotonated Hpdcd2 − ligands to generate a 1D isolated tube and 2D highly undulating layer, respectively.Display Omitted► 1D isolated tube and 2D highly undulating layer were prepared by bbi and H3pdcd. ► Compounds 1 and 2 show a 1D→2D and 2D→3D interdigital structure, respectively. ► The luminescent property of 1 has been investigated.
Keywords: Coordination polymer; Tube; Meso-helical chain; Interdigitation; Conformation;

Magnetic and ferroelectric properties of two Co(II) complexes based on flexible bis(imidazole) ligands by Yue Wang; Fang-Hua Zhao; Ai-Hua Shi; Yun-Xia Che; Ji-Min Zheng (23-26).
Two Co(II) complexes, [Co(bimb)(L1)2] (1) and [Co(bix)(L2)] (2) (bimb = 1,4-bis(imidazol-1–yl)-butane, bix = 1,4-bis(imidazol-1-yl-methylene)-benzene, HL1  = 3,5-dinitro-benzoic acid, H2L2  =  o-phthalic acid), have been successfully prepared based on achiral flexible bis(imidazole) ligands via spontaneous resolution. Complexes 1 and 2 crystallize in the asymmetrical monoclinic with P21 and Cc space groups, respectively. Interestingly, magnetic studies reveal that complex 1 demonstrates dominant ferromagnetic behavior and complex 2 displays spin-canting behavior. More interestingly, both complexes 1 and 2 exhibit ferroelectric features representing electric hysteresis loops with the saturation polarization (P s) of ca. 0.085 μC cm− 2 and 0.141 μC cm− 2.This work reported two complexes based on flexible bis(imidazole) ligands with aromatic carboxylate ligands. And the focus on their magnetic and ferroelectric properties has been investigated in detail.Display Omitted► Two complexes based on flexible bis(imidazole) ligands have been presented. ► Both ferromagnetic and ferroelectric behaviors were observed for complex 1. ► Spin-canting and ferroelectric behaviors were observed for complex 2.
Keywords: Chiral complex; Flexible bis(imidazole) ligands; Magnetic property; Ferroelectric property;

Blue to orange emitters; palladium(0) monodentate phosphine complexes by Takuma Ohkubo; Koichiro Takao; Taro Tsubomura (27-29).
Photoluminescence properties of palladium(0) complexes bearing monodentate phosphines are described. [Pd(P(o-tol)3)2] (o-tol =  ortho-tolyl) emits relatively strong blue luminescence in the solid state. Whereas, [Pd(PCyPh2)3] (Cy = cyclohexyl) and [Pd(PCy3)2] show orange luminescence with a large Stokes-shift. The crystal structure analysis of [Pd(PCyPh2)3] reveals the trigonal planar geometry around the palladium atom.Palladium(0) complexes bearing monodentate phosphines emit blue to orange luminescence. [Pd(P(o-tol)3)2] shows blue emission in the solid state. Both of [Pd(PCyPh2)3] and [Pd(PCy3)2] show orange emissions with a large Stokes-shift in the solid state.Display Omitted► Blue to orange luminescence has been observed for palladium(0) complexes bearing monodentate phosphines. ► Blue luminescence was found for [Pd(P(o-tol3)2)]. ► Other two complexes show orange emission with an unusual large Stokes-shift.
Keywords: Luminescence; Palladium(0); Phosphine complexes;

A new three-dimensional (3D) metal-organic framework (MOF) [Cd(tpa)Cl](CH3)4  N+ (1; tpa = 1, 4-terephthalic acid) with unusual Cd2 (COO)4Cl2 building block has been solvothermally synthesized and structurally characterized by the aid of single crystal X-ray diffraction, powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA) Elemental analysis (EA) and Infrared Spectroscopy (IR). The Cd2(COO)4Cl2 building block can be simplified as 4-connected or two 3-connected nods in different ways, correspondingly, the compound 1 exhibits 4-connected dia or 3-connected ths structural topology.Presented here is a new 4-connected dia or 3-connected ths cadmium-organic framework with unusual Cd2(COO)4Cl2 building blocks.Display Omitted► A metal-organic framework with unusual Cd2(COO)4Cl2 building blocks. ► A metal-organic framework with dia or ths structural topology. ► Solvothermal synthesis of a photoluminescent compound.
Keywords: Metal-organic framework; Cadmium; Topology; SBUs; Crystal structure;

Synthesis, structure and near-infrared (NIR) luminescence of series of Zn2Ln (Ln = Nd, Yb or Er) complexes based on the Salen-type Schiff-base ligand with the flexible linker by Wei-Xu Feng; Ya-Ni Hui; Guo-Xiang Shi; Dan Zou; Xing-Qiang Lü; Ji-Rong Song; Dai-Di Fan; Wai-Kwok Wong; Richard A. Jones (33-36).
With the Zn-Schiff-base [ZnL(CH3CN)] from the Salen-type Schiff-base ligand H2L (H2L = N,N′-bis(3-methoxy-salicylidene)cyclohexane-1,2-diamine) with the flexible linker as the precursor, a series of hetero-trinuclear Zn2Ln complexes [Zn2Ln(L)2(Cl)3] (Ln = Nd, 1; Ln = Yb, 2; Ln = Er, 3; Ln = Gd, 4) are obtained by the further reaction with LnCl3·6H2O, respectively. The results of their photophysical studies show that the strong and characteristic NIR luminescence with emissive lifetimes in the microsecond range, has been sensitized from the excited state (both 1LC and 3LC) of the ligand due to the effective intramolecular energy transfer.Synthesis, structure and near-infrared (NIR) luminescence of series of Zn2Ln (Ln = Nd, Yb or Er) complexes based on the Salen-type Schiff-base ligand with the flexible linker are reported.Display Omitted► Trinuclear Zn2Ln complexes based on the Salen-type Schiff-base ligand with the flexible linker. ► Effective sensitization and efficient energy transfer. ► Enhanced near-infrared luminescent properties.
Keywords: Zn2Ln arrayed Schiff-base complexes; Sensitization and energy transfer; NIR luminescent properties;

Main group metal complex [Bi(HL)(NO3)3] (1), where HL = 2-acetylpyrazine N(4)-pyridylthiosemicarbazone, has been synthesized and characterized by elemental analysis, IR, MS and single-crystal X-ray diffraction studies. The interesting monomeric 8-coordinate bismuth(III) complex 1 is depicted with one electron pair (6 s2) of the bismuth(III) atom, one N2S tridentate neutral thiosemicarbazone, two monodentate and one bidentate nitrate ions, respectively. In vitro biological studies have indicated that the bismuth complex 1 has shown effective antibacterial and anticancer activities especially with MIC = 15.6 μg/mL against Gram positive bacteria Bacillus cereus and IC50  = 1.6 μM against K562 leukemia cell lines, respectively, comparable to positive control.Main group metal complex [Bi(HL)(NO3)3] (1), where HL = 2-acetylpyrazine N(4)-pyridylthiosemicarbazone, has been synthesized and structurally characterized. Formation of 8-coordinated structure of the bismuth(III) atom is unusual and interesting. Biological studies have indicated that the bismuth(III) complex shown effective antibacterial and anticancer activities, especially with MIC = 15.6 μg/mL against Gram positive bacteria Bacillus cereus and IC50  = 1.6 μM against K562 leukemia cell lines, respectively, comparable to positive control.Display Omitted► Bismuth(III) complex [Bi(HL)(NO3)3] (1) has been synthesized and characterized. ► Formation of 8-coordinated structure of the bismuth(III) atom is unusual. ► The bismuth complex 1 shown effective biological activities. ► These results are encouraging its further screening and evaluation of mechanism.
Keywords: Thiosemicarbazone; Bismuth (III); Crystal structure; Cytotoxic activity;

Effective enhancement of near-infrared emission by carbazole modification in the Zn–Nd bimetallic Schiff-base complexes by Shunsheng Zhao; Xiangrong Liu; Weixu Feng; Xingqiang Lü; Wai-Yeung Wong; Wai-Kwok Wong (41-45).
With ZnL1 or ZnL2 from the simple Salen-type Schiff-base ligand H2L1 (H2L1═N,N′-bis(3-methoxysalicylidene)-ethylene-1,2-diamine) or the carbazole-modified Salen-type Schiff-base ligand H2L2 (H2L2═N,N′-bis(3-methoxy-5-{2-[4-(N-carbazyl)-phenyl]-ethynyl}-ethylene-1,2-diamine) as the precursor, two series of four bimetallic ZnLn complexes (Ln=Nd(1 or 3), Ln=Gd (2 or 4) are obtained, respectively. The photophysical properties results showed that the sensitization from the excited state (1LC and 3LC) of the ligand H2L1 or H2L2 and the effective energy transfer of Zn2+-Schiff-base (ZnL1 or ZnL2) to the Nd3+ ion for the NIR luminescence were realized, respectively. Especially through the cabarzole modification, the improved NIR luminescence of the ZnNd complex 3 was observed due to the realization of the energy level's match of the excited state of the chromophore to the Nd3+ ion's exciting state.In the Zn–Nd Schiff-base complexes from H2L1 or the carbazole-modified H2L2, through the carbazole modification, the improved NIR luminescence of the ZnNd complex 3 was observed, due to the avoiding of the luminescent quenching effect arising from OH-, CH- or NH-oscillators of the solvates around the Nd3+ ion in combination with the realization of the energy level's match of the excited state of the chromophore to the Nd3+ ion's exciting state.Display Omitted► Carbazole-modified Salen-type Schiff-base ligand. ► Effective sensitization and efficient energy transfer. ► Enhancement of near-infrared luminescence of the Zn–Nd binuclear Schiff-base complexes.
Keywords: Carbazole modification; ZnNd binuclear Schiff-base complex; Sensitization and energy transfer; Enhanced NIR luminescence;

Cobalt(II) metamagnet built from ferromagnetic chains with mixed bis(azido)(carboxylate) bridges by Yan-Qing Wen; Yu Ma; Yan-Qin Wang; Xiu-Mei Zhang; En-Qing Gao (46-49).
A new one-dimensional Co(II) coordination polymer, Co(L)(N3)2 (L = pyridinio-N-acetate), has been synthesized by a diffusion method and characterized by single crystal X-ray diffraction. In the compound, Co(II) ions are linked by mixed triple bridges (two end-on azides and a syn–syn carboxylate), which transmit ferromagnetic coupling with J = 13.96 cm− 1. The compound exhibits field-induced metamagnetic behaviors below TN  = 2.3 K with Hc = 100 Oe, due to weak antiferromagnetic interactions between chains.The mixed bis(azido)(carboxylate) triple bridges in the new cobalt(II) chain compound derived from a zwitterionic carboxylate ligand induce ferromagnetic coupling and the compound exhibits metamagnetic behaviors.Display Omitted► Bis(azido)(carboxylato)-bridged magnetic systems from zwitterionic ligands. ► The mixed bridges mediate ferromagnetic exchange between Co(II) ions. ► Metamagnetism due to competitive intrachain and interchain interactions.
Keywords: Cobalt; Azide; Carboxylate; Metamagnetic properties;

A heterometallic triple-chain complex [CuTb2(mal)4(H2O)6]·2H2O (CuTb2, H2mal =  d-malic acid) and its isomorphous CuY2 and ZnTb2 have been prepared and characterized, whose magnetic properties are studied by comparison with its analogues. The results indicate that the Cu⋯Tb interactions in CuTb2 are antiferromagnetic.A heterometallic triple-chain complex [CuTb2(mal)4(H2O)6]·2H2O (CuTb2 , H2mal = D-malic acid) and its isomorphous CuY2 and ZnTb2 have been prepared and characterized, whose magnetic properties are studied by comparison with its analogues. The results indicate that the Cu⋯Tb interactions in CuTb2 are antiferromagnetic.Display Omitted► One-Dimensional heterometallic triple-chain complexes with both transition metal and lanthanide ions are very few and novel. ► The substitution method by diamagnetic ions is very effective in investigating the nature of Cu2+···Tb3+ interactions. ► Antiferromagnetic couplings exist between Cu2+ and Tb3+ ions in CuTb2 complex.
Keywords: Heterometallic complex; Triple-chain; Crystal structure; Magnetic properties;

The interactions between 2,6-diacetylpyridine bis-4-N-ethylthiosemicarbazone (1) and ten lanthanide triflates have been studied by means of electrospray ionization mass spectrometry. The aim of this work is to gain a better insight into the coordination trends of thiosemicarbazones towards lanthanides. Thiosemicarbazone ligand 1 forms with lanthanides stable complexes, which can be observed in the ESI spectra.The lanthanide salts, trifluoromethanesulfonates(triflates) La(CF3SO3)3, and the ligand, 2,6-diacetylpyridine bis-4-N-ethylthiosemicarbazone 1, in acetonitrile were infused into the ESI source and positive mass spectra have been obtained.Display Omitted► Electrospray ionization mass spectra of solutions containing thiosemicarbazone, lanthanide triflate and acetonitrile. ► Thiosemicarbazone-lanthanide complexes detected and their structure analyzed. ► Ligand's affinity to fluoride anions confirmed. ► Thiosemicarbazone/lanthanide triflates complexation mainly through deprotonation of the ligand.
Keywords: Lanthanide triflates; Complexes; Mass spectra; Electrospray ionization; Thiosemicarbazone;

Magnesium catalysts incorporated by sterically bulky benzotriazole-phenoxide ligands ( CMe2Ph BTP , t-Bu BTP and TMCl BTP ) are synthesized and structurally characterized. The reaction of Mg n Bu2 with CMe2Ph BTP-H (2.0 mol Eq) in THF produces penta-coordinated monomeric magnesium complex [( CMe2Ph BTP)2Mg(THF)] (1). However, six-coordinated bis-adduct magnesium complexes [( t-Bu BTP)2Mg(THF)2] (2) and [( TMCl BTP)2 Mg(THF)2] (3) result from treatments of Mg n Bu2 with t-Bu BTP-H and TMCl BTP-H in THF under the same stoichiometric proportion, in which each Mg center is coordinated by two THF molecules. Optical properties and catalytic studies for l-lactide polymerizations of magnesium complexes 13 are investigated. Magnesium complex 3 catalyzes the ring-opening polymerization effectively not only in a “controlled” fashion but also in an “immortal” manner, giving polymers with the expected molecular weights and narrow molecular weight distributions.Magnesium complexes derived from sterically bulky benzotriazole-phenoxide ligands ( CMe2Ph BTP , t-Bu BTP and TMCl BTP ) were synthesized and fully characterized. Complex 3 is an active catalyst for the ring-opening polymerization of l-lactide in the presence of 9-anthracenemethanol (9-AnOH), giving polymers with expected molecular weights and narrow PDIs.Display Omitted► Magnesium complexes supported by sterically bulky BTP ligands are synthesized and structurally characterized. ► Monomeric Mg complex 1 emits the highest green fluorescence in solution among these complexes. ► Complex 3 catalyzes the polymerization of l-lactide with the “controlled” and “immortal” characters.
Keywords: Magnesium complex; Catalyst; N,O-Bidentate; Ring-opening polymerization; Photoluminescence; l-Lactide;

Synthesis, structure and magnetic properties of neutral Ni (II) tri-tert-butoxysilanethiolate cluster by Agnieszka Pladzyk; Łukasz Ponikiewski; Yanhua Lan; Annie K. Powell (66-69).
A novel nickel(II) cluster [Ni6(μ-O)6{SSi(tBuO)3}6(H2O)6(NH3)4] 1 has been synthesized in reaction of NiCl2⋅ 6H2O with tri-tert-butoxysilanethiol and ammonia in water solution. The magnetic measurements show the presence of strong antiferromagnetic interactions between magnetic centers.A neutral hexanuclear oxo-bridged nickel(II) cluster 1 has been obtained in the reaction of NiCl2  6H2O, ammonia and tri-tert-butoxysilanethiol in water. Ni(II) ions in 1 are coordinated by ammonia, water and (tBuO)3SiS -. Magnetic measurements show strong antiferromagnetic interactions between the six Ni(II) ions with a zero total spin ground state.Display Omitted► A neutral hexanuclear oxo-bridged nickel (II) cluster has been synthesized. ► Metal ions coordinated by ammonia, water and (tBuO)3SiS. ► The cluster exhibits the topology of a face-sharing double cubane. ► Magnetic measurements show strong antiferromagnetic interactions between Ni (II) ions. ► The total spin ground state of the compound is zero.
Keywords: Nickel clusters; Tri-tert-butoxysilanethiol; Crystal structure; Magnetic property;

High spin to low spin change induced by reductive chemistry with iron-substituted Dawson polyoxometalate by Daniela Cioloboc; Adrian-Raul Tomşa; Grigore Damian; Radu Silaghi-Dumitrescu (70-72).
Chemical reduction of an iron(III) substituted Dawson 5-molybdo-12-tungsto-2-phosphate α2-K7[Fe(H2O)P2Mo5W12O61]⋅ 17H2O complex, with dithionite in aqueous solution is reported alongside with similar data for the monolacunary Dawson molybdo-tungsto-diphosphates α2-[P2Mo5W12O61]10 −. UV–vis absorption and low-temperature EPR (electron paramagnetic resonance) spectra indicate several distinct species and an unprecedented change of spin state at the ferric center, induced indirectly by reduction of the polyoxometalate framework.EPR and UV–vis spectra reveal several redox states accessible in a novel iron-substituted Dawson polyoxometalate, including an unprecedented spin-state changeDisplay Omitted► Reduced forms of iron-containing polyoxometalates are detected by UV–vis and EPR. ► Multiple-step reductions are demonstrated. ► EPR data reveal an unusual spin-state shift at the iron during the reduction of the POM.
Keywords: Polyoxometalate; Spin state; Iron; EPR;

Novel terbium luminescent complexes with o-phosphorylated phenolate ligands by Sergey Shuvaev; Oxana Kotova; Valentina Utochnikova; Andrey Vaschenko; Lada Puntus; Vladimir Baulin; Natalia Kuzmina; Aslan Tzivadze (73-76).
Lanthanide complexes with ortho-phosphorylated phenolate ligands LnL3 (Ln = Eu, Tb, Lu; HL1  = 2-di(p-tolyl)phosphorylphenol; HL2  = 2-diphenylphosphoryl-4-ethylphenol) were synthesized for the first time and characterized by elemental analysis, FTIR, 1H, 31P NMR spectroscopy, LDI-TOF mass-spectrometry. The energy gap between the triplet energy level and the corresponding resonance level of a lanthanide ion (5D1 for Eu3+ and 5D4 for Tb3+) is optimal for luminescence sensitization of only terbium ions. Bright green photo- and electroluminescence of terbium complexes was demonstrated.The interaction between phosphorylated phenols (HL) and sodium hydroxide leads to formation of sodium phosphorylated phenolate (NaL). Reaction between sodium phosphorylated phenolate and inorganic salts of lanthanides (LnCl3·nH2O) leads to formation of lanthanide complexes LnL3.Display Omitted► Lanthanide complexes of aromatic o-phosphorylated phenols were synthesized. ► Luminescent and volatility properties of lanthanide complexes were investigated. ► Thin film of terbium complex was tested as an active layer of OLED.
Keywords: Phosphorylated phenol; Lanthanide complexes; Photoluminescence; Electroluminescence;

Efficient DNA photocleavage promoted by a Tb(III) complex by Angélica Cavalett; Tiago Bortolotto; Patrícia Rabêlo Silva; Gilmar Conte; Hugo Gallardo; Hernán Terenzi (77-80).
This work demonstrates the efficient photocleavage of DNA induced by a terbium complex. Mechanistic studies and DNA groove binding dependence were performed to better understand the photo-cleavage reaction, suggesting the presence of oxygen and carbon-centered radicals in the strand scission event. Furthermore, kinetic analyses were also achieved. The DNA photocleavage promoted by the title complex proceeds with a k obs of ~ 10.2 h− 1, a reaction rate useful in molecular biology practices, with a t 1/2 of 4 min. This complex emerges as a new example of lanthanide compound with DNA cleavage ability by a non-hydrolytic mechanism.Great efficiency in DNA cleavage promoted by Tb(tdzp)(acac)3 complex was achieved with UV-light illumination, without significant activity under dark conditions.Display Omitted► The reported complex shows an efficient DNA cleavage activity under UV-A light. ► No activity was observed without UV-A light irradiation. ► During strand scission event radical species are produced. ► This complex is able to cleave DNA with a rate constant of 0.17 min− 1 which represents a half-life of only 4 min.
Keywords: Terbium complex; Lanthanide complex; DNA photocleavage; UV-light; Photodynamic therapy (PDT);

Treatment of [(TPA)FeII(CH3CN)2]2+ (TPA = tris(2-pyridylmethyl)amine) with excess (≥ 2 Eq) of 3-chloroperoxybenzoic acid (mCPBA) in semi-frozen acetonitrile in liquid N2 vapour generates a rhombic EPR signal assigned to the S  = ½ low spin acylperoxoiron(III) species [(TPA)Fe(O3CC6H4-3Cl)(CH3CN)]2+ 5; the elusive precursor on the pathway to [(TPA)FeIII(5-chlorosalicylate)]+ 4 via putative [(TPA)FeV(O)(O2CC6H4-3Cl)]2+. Formation of cyclohexene epoxide in the presence of added cyclohexene at low temperatures (<−40 °C) suggests that intermolecular alkene epoxidation competes successfully with the intramolecular reactions involving 5 to generate 4.Treatment of [(TPA)Fe(CH3CN)2]2+ 1 with excess (≥ 2 Eq) of 3-chloroperoxybenzoic acid (mCPBA) in semi-frozen acetonitrile generates an S  = ½ EPR signal assigned to the low spin acylperoxo iron(III) species; [(TPA)Fe(O3CC6H4-3Cl)(CH3CN)]2+ 5; the elusive precursor to putative ‘(TPA)FeV(O)’ on the pathway to [(TPA)FeIII(5-chlorosalicylate)]+. Solutions of 5 are also active in promoting cyclohexene epoxidation.Display Omitted► Mixing [(TPA)FeII(CH3CN)2]2+ with ≥2eq mCPBA in semi-frozen acetonitrile forms [(TPA)Fe(O3CC6H4-3Cl)(CH3CN)]2+ 5. ► Detection (by EPR) of 5 for the first time is as a result of mixing the reagents in the semi-frozen acetonitrile medium. ► 5 is the direct precursor of putative ‘(TPA)FeV(O)2+’ on the pathway to [(TPA)FeIII(5-Cl-salicylate)]+, the final product. ► Generation of cyclohexene epoxide shows that intermolecular alkene epoxidation competes with intramolecular CH O-insertion. ► The findings cannot rule out the possibility that acylperoxoiron(III) complexes can themselves promote alkene epoxidation.
Keywords: TPA; Acylperoxoiron; EPR; Cyclohexene epoxidation; mCPBA; Salicylate;

Synthesis, X-ray structure and oxidation catalysis of a oxido–peroxido molybdenum(VI) complex with a tridentate Schiff base ligand by Mojtaba Bagherzadeh; Mojtaba Amini; Hadi Parastar; Mehdi Jalali-Heravi; Arkady Ellern; L. Keith Woo (86-89).
A new oxido–peroxido molybdenum(VI) complex [MoO(O2)L(CH3OH)] was synthesized, using salicylidene benzoyl hydrazine as tridentate ONO donor Schiff base ligand (H2L). The complex has been characterized by elemental analysis, IR, 1H NMR, molar conductance data, and finally by X-ray structure analysis. This complex functions as facile olefin epoxidation catalyst with hydrogen peroxide (H2O2) as terminal oxidant and sodium hydrogen carbonate (NaHCO3) as a co-catalyst at room temperature. Catalytic potentiality of complex is also exhibited in oxidation of sulfides. The catalyst show very much efficient reactivity in the oxidation reactions giving high yield, turnover number (TON) and selectivity.A new oxo–peroxo molybdenum(VI) complex [MoO(O2)L(CH3OH)] was synthesized and characterized. The complex efficiently catalyzes the selective oxidation of sulfides and olfins to the corresponding sulfoxides and epoxides using UHP and H2O2 respectively as an oxidant.Display Omitted► Molybdenum(VI) oxo-peroxo complex is applied in oxidation of olefins and sulfides. ► Hydrogen peroxide (H2O2) and urea hydrogen peroxide (UHP) as oxidant. ► Excellent yield, high TONs and selectivity has been achieved.
Keywords: Oxido–peroxido complex; Molybdenum; Olefin epoxidation; Sulfide oxidation;

The synthesis of hydroxyapatite nanoparticles is reported using a hydrothermal microemulsion technique with calcium nitrate tetrahydrate and diammonium hydrogen phosphate as precursors is reported. The advantage of this proposed technique over other previously reported techniques is that particles with controlled size and morphology can be obtained with a new microemulsion with cetyltrimethylammonium bromide (CTAB)/toluene/n-butanol/water as a nanoreactor. X-ray diffraction (XRD) analysis showed that the hydrothermal microemulsion produced powders with phase-pure hexagonal hydroxyapatite. Transmission electron microscopy (TEM) showed that nanoparticles with both defined and undefined shapes can be obtained. Hydroxyapatite nanoparticles with a typical hexagonal prism-like morphology were obtained when microemulsion parameters such as the water to surfactant molar ratio (W0) and the cosurfactant to surfactant molar ratio (P0) were adjusted to defined values. The effects of changes in microemulsion parameters (W0 and P0) on sizes calculated using both transmission electron microscopy (TEM) and dynamic light scattering (DLS) were also investigated; the observed trends are discussed in terms of the interaction between amphiphilic molecules and hydroxyapatite precursor ions at the water–oil (W/O) interfaces.The synthesis of hydroxyapatite nanoparticles is reported using a hydrothermal microemulsion technique. Particles with controlled size and morphology were obtained. X-ray diffraction (XRD) analysis showed that the hydrothermal microemulsion produced powders with phase-pure hexagonal hydroxyapatite. Transmission electron microscopy (TEM) showed that nanoparticles with both defined and undefined shapes can be obtained.Display Omitted► Hydroxyapatite nanoparticles were synthesised using a hydrothermal microemulsion technique. ► Cetyltrimethylammonium bromide (CTAB)/toluene/n-butanol/water as nanoreactor. ► Water to surfactant molar ratio (W0) and cosurfactant to surfactant molar ratio (P0). ► Interaction between amphiphilic molecules and hydroxyapatite precursor ions at the water–oil (W/O) interfaces.
Keywords: Hydroxyapatite nanoparticle; Particle size; Hydrothermal synthesis; Microemulsion parameter;

A highly selective rhodamine based turn-on optical sensor for Fe3+ by Ziya Aydin; Yibin Wei; Maolin Guo (93-96).
A reversible turn-on sensor (Rh–OH–Rh) which can selectively detect Fe3+ in solution has been developed. The sensor combines two rhodamine moieties with a 3-oxygen Fe3+ receptor to provide excellent selectivity for Fe3+ over a range of biologically relevant metal ions. It binds Fe3+ in a 1:1 stoichiometry with an apparent binding constant 5.2 × 106  M− 1 (log K = 5.28) in ACN/DMF (9/1 v/v) solution. The sensor displays distinct “on–off” changes in color and fluorescence upon the alteration of free Fe3+ levels in solution with a reversible response and little interference with other biological relevant metal ions.A reversible turn-on sensor (Rh–OH–Rh) which can selectively detect Fe3+ in solution based on distinct “on–off” changes in color and fluorescence has been developed.Display Omitted► A new Fe3+-selective turn-on optical sensor with a 3-oxygen Fe3+ receptor was designed and synthesized. ► The sensor binds Fe3+ in a 1:1 stoichiometry with an apparent binding constant 5.2 × 106 M–1 in solution. ► The sensor displays distinct "on-off" color and fluorescence changes upon the alteration of free Fe3+ levels in solution. ► The sensor has excellent selectivity for Fe3+, with little interference from other metal ions.
Keywords: Fluorescent sensor; Fe3+; Rhodamine B; Chemosensor; Turn-on;

Uniform europium-based infinite coordination polymer submicrospheres: Fast microwave synthesis and characterization by Dong Zhao; Lei Wang; Yuan Li; Linfei Zhang; Yunhai Lv; Shengliang Zhong (97-100).
Uniform europium-based infinite coordination polymer (ICP) submicrospheres have been prepared via a facile and fast microwave heating method in 5 min, with pyridine-2, 5-dicarboxylic acid and europium nitrate as reagents and N, N-dimethylformamide (DMF) as solvent. The products were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Fourier-transform infrared spectroscopy (FTIR). Thermogravimetric (TG) and derivative thermogravimetric analysis (DTG) were also carried out. XRD results reveal that the product is amorphous. SEM and TEM results show that the submicrospheres are with diameters of 200–400 nm. Furthermore, the surface of the microspheres is smooth and the submicrospheres are solid. Strong red emission centering at 618 nm was observed in the europium-based ICP microspheres on excitation with 394 nm UV light. This method may be employed to the preparation of other coordination polymers micro/nanostructures.Uniform europium-based infinite coordination polymer submicrospheres have been prepared from pyridine-2, 5-dicarboxylic acid and europium nitrate via a facile and fast microwave heating method in 5 min,Display Omitted► Infinite coordination polymer spheres have been prepared via a facile and fast microwave method. ► The spheres are uniform and are with diameters of 200–400 nm. ► Strong red emission was realized in the submicrospheres.
Keywords: Microwave; Coordination polymer; Amorphous materials; Rare earth;

A new luminescent Cu(I) complex stabilized by Cu⋅⋅⋅Cu interactions by Xin Zhang; Jian-Kai Cheng; Ming-Jian Zhang; Yuan-Gen Yao (101-104).
A novel luminescent Cu(I) compound, [Cu(HtrzS)]n (1 HtrzSH=1H-1,2,4-triazole-3-thiol), was hydrothermally synthesized, which features a two-dimensional (2D) inorganic–organic hybrid framework containing a inorganic [CuS]n layer. Further, this 2D framework is connected by the intermolecular hydrogen bonds into a three-dimensional (3D) supramolecular framework. Optical diffuse reflectance study reveals an optical band gap of 3.44 eV, making it a wide band gap semiconductor. Moreover, this compound exhibits strong photoluminescence at room temperature. The densities of states (DOS) calculations reveal that luminescence emission bands of the compound originate from the ligand-to-metal charge transfer.Presented here is a new luminescent Cu(I) complex, [Cu(HtrzS)]n (1 HtrzSH = 1H-1,2,4-triazole-3-thiol), which features a two-dimensional (2D) inorganic–organic hybrid framework containing a inorganic [CuS]n layer.Display Omitted► A new luminescent Cu(I) was synthesized and characterized. ► The complex features an inorganic [CuS]n layer. ► Optical diffuse reflectance study reveals an optical band gap of 3.44 eV.
Keywords: Copper(I) compound; Hybrid framework; Photoluminescence; Supramolecular framework;

Unusual high photoassisted quantum yields for cis-to-trans254 nm  = 0.27 ± 0.05) isomerization of CNstpy coordinated to fac-[Re(CO)3(phen)(CNstpy)]+ were determined along with trans-to-cis ones (Φ313 nm  = 0.58 ± 0.02; Φ365 nm  = 0.61 ± 0.06; Φ404 nm  = 0.42 ± 0.02). Additionally, in contrast to other similar rhenium(I) complexes, the cis photoproduct is quasi non-emissive and comparable to the trans-complex. The cis-to-trans photoisomerization is due to the deactivation from the ILcis-CNstpy excited state in competition to the usual 3MLCTRe→phen luminescence. These efficient cis to trans and trans to cis photoisomerization can be conveniently used in light powered molecular machines.The Graphical Abstract summarizes all photoisomerization quantum yields determined for fac-[Re(CO)3(phen)(CNstpy)]+, as well as the trans- and cis-complex structures. It evidences the capacity of changing the majoritarian isomer by changing the incident light energy. These efficient cis to trans and trans to cis photoisomerization can be conveniently used in light powered molecular machines.Display Omitted► Efficient photoresponsive Re(I) compound applicable in molecular machines. ► trans/cis apparent and true photoisomerization quantum yields for fac-[Re(CO)3(phen)(CNstpy)]+. ► Unusual photophysical properties of fac-[Re(CO)3(phen)(cis-CNstpy)]+.
Keywords: Rhenium; Photochemistry; Photophysics; True quantum yield; Stilbene-like ligand photoisomerization;

Two coordination polymers, [M(Fpht)tib]·H2O (M = Cd 1, Co 2; H2Fpht = 3-fluorophthalic acid and tib = 1,3,5-tris(1-imidazolyl)benzene) have been synthesized and structurally characterized by single crystal X-ray diffraction. They possess unusual double layer structures constructed from M–Fpht helices and (3, 3) M–tib honeycom layers. The fluorescence of the complexes maybe arise from the intraligand π–π transition.Two coordination polymers, [M(Fpht)tib]•H2O (M = Cd 1, Co 2; H2Fpht = 3- fluorophthalic acid and tib = 1,3,5-tris(1-imidazolyl)benzene) have been synthesized and structurally characterized. They possess unusual double layer structures constructed from M-Fpht helices and (3, 3) M-tib honeycom layers.Display Omitted► Unusual 2D double layer structure is constructed from Cd(II)/Co(II) ions with 3-fluorophthalic acid (H2Fpht) and 1,3,5-tris(1-imidazolyl)benzene) (tib). ► Each tib ligand connects three M(II) ions and each M(II) ion connects three tib ligands to generate an (3, 3) M–tib honeycom layer. ► M(II) ions are linked together by the Fpht ligands to form M–Fpht right- and left-handed helical chains. ► 3D supramolecular network is formed by C―H…π or π…π interaction.
Keywords: Coordination polymer; 3-Fluorophthalic acid; 1,3,5-Tris(1-imidazolyl)benzene; Crystal structure; Fluorescence;

Three lanthanide-radical complexes: Synthesis, structure and magnetic properties by Chao Wang; Ya-li Wang; Zi-xuan Qin; Yue Ma; Qing-lun Wang; Li-cun Li; Dai-zheng Liao (112-116).
Three new lanthanide-radical complexes containing the same radical ligand were successfully synthesized, which all display radical-Ln(III)-radical (Ln = Pr (1), Gd (2), Ho(3)) tri-spin structures. The magnetic studies revealed that, for complex 2, the interactions between the Gd(III) ion and radical are ferromagnetic, while the interaction between two radicals is antiferromagnetic. In complexes 1 and 3, antiferromagnetic couplings exist between the lanthanide ions and radicals.The crystal structures and magnetic properties of three new lanthanide-radical complexes were fully characterized. Complex based on Gd(III) ion have both ferromagnetic and antiferromagnetic interactions in one molecule, and other complexes were roughly estimated through a simplified model.Display Omitted► Three lanthanide-radical complexes were successfully synthesized. ► Both ferromagnetic and antiferromagnetic interactions exist in complex 2. ► Simplified models were carried out to evaluate the coupling in complexes 1 and 3.
Keywords: Nitronyl nitroxide radical; Lanthanides; Crystal structure; Magnetic properties;

Synthesis, structures and guest molecules adsorption of Zn(II)-bridged metal-organic polymers by Xiu-Ting Wang; Yue-Ling Bai; Feifei Xing; Min Shao; Shourong Zhu (117-121).
Two coordination polymers {[Zn(fum)(btmb)]·3H2O}n (1) and {[Zn(2,3-pzdc)(tttmb)(H2O)2]·H2O}n (2) (H2fum = fumaric acid, btmb = 4,4′-bis(1,2,4-triazol-1-ylmethyl)biphenyl, 2,3-H2pzdc = 2,3-pyrazinedicarboxylic acid, tttmb = 1,3,5-tris(triazol-1-ylmethyl)-2,4,6-trimethylbenzene) have been synthesized and structurally characterized. Compound 1 is a two-fold interpenetrating 2D network; significant π–π interactions in adjacent layers finally result in a 3D supramolecular framework with 14.167 × 7.831 Å channel. Compound 2 is a 1D chain. The guest molecules (fluorescein and phenylfluorone) adsorption behaviors of 1 and luminescent properties of 1 and 2 have been investigated.Two coordination polymers {[Zn(fum)(btmb)]·3H2O}n (1) and {[Zn(2,3-pzdc)(tttmb)(H2O)2]·H2O}n (2) (H2fum = fumaric acid, btmb = 4,4′-bis(1,2,4-triazol-1-ylmethyl)biphenyl, 2,3-H2pzdc = 2,3-pyrazinedicarboxylic acid, tttmb = 1,3,5-tris(triazol-1-ylmethyl)-2,4,6-trimethylbenzene) have been synthesized and structurally characterized. 1 was a two-fold interpenetrating 2D network and ultimately formed a 3D supramolecular framework with large channel from significant π–π interactions in adjacent layers, which can respectively adsorb guest molecules of fluorescein and phenylfluorone. The adsorption behaviors were approved by elemental analysis, PXRD and luminescent.Display Omitted► Compound 1 is a two-fold interpenetrating 2D network, which finally results in a 3D supramolecular framework with large channel by significant π–π interactions in adjacent layers. ► Compound 1 can adsorb guest molecules of fluorescein and phenylfluorone, respectively. ► The adsorption behaviors were approved by elemental analysis, PXRD and luminescent.
Keywords: Polymers; Crystal structures; Guest molecules adsorption; Luminescent properties;

The zwitterionic ligand H2Bci [H2Bci = 1,3-bis(4-carboxybenzyl)-1H-imidazolium] was formed via in situ reaction. Its Eu(III)-organic framework, {[Eu(Bci)2]Cl}n (1), was obtained under hydrothermal conditions. Complex 1 exhibits a 3-fold interpenetrated diamondoid network with double-bridged connectors. Its solid-state luminescent behavior was investigated at room temperature.A 3D Eu(II) coordination polymer that exhibits a 3-fold interpenetrated diamondoid network with double-bridged connectors based on a zwitterionic ligand was formed via in situ reaction.Display Omitted► A zwitterionic ligand is formed by in situ reaction. ► A framework exhibits a diamondoid network with double-bridged connectors. ► The first Eu(II) coordination polymer based on 1,3-bis(4-carboxybenzyl)-1H-imidazolium.
Keywords: Zwitterionic ligand; Eu(III) coordination polymer; Solid-state luminescent;

Two new silver(I) complexes [Ag2(μ-dppb)2(CF3SO3)2] (1) and {[Ag2(dppb)3](CF3SO3)2•(4,4′-bipy)•(CH3CN)2} n (2) (dppb = bis(diphenylphosphino)butane, 4,4′-bipy = 4,4′-bipyridine) which contain dppb and trifluoromethanesulfonate anions have been synthesized and characterized by IR, X-ray crystallography, 1H NMR, 31P NMR spectroscopy and luminescence. Complex 1 and 4,4′-bipy reacted in the solution CH3CN to get complex 2. In the reaction, the 14-membered ring [Ag2(μ-dppb)2] of complex 1 is opened to form the “honeycomb” (6, 3) network structure of complex 2. In 2, each [Ag6(μ-dppb) 6] 6+ ring hosts two counterions, one 4,4′-bipy and two acetonitrile guest molecules.Induced by nitrogen heterocyclic ligands, [Ag2(dppb)2(CF3SO3)2] (1) was obtained. The 14-membered ring [Ag2(μ-dppb)2] of 1 is opened to form (6,3) network structure of {[Ag2(dppb)3](CF3SO3)2•(4,4′-bipy)•(CH3CN)2} n (2). In 2, each [Ag6(μ-dppb) 6] 6+ ring hosts CF3SO3 , 4,4’-bipy and acetonitrile molecules. 12 were characterized by IR, luminescence, 1H NMR, 31P NMR, and X-ray crystal diffraction.Display Omitted► The (6,3) network structure of 2 is formed by the ring-opening reaction of 1 with 4,4′-bipyridine. ► In 2, each [Ag6(μ-dppb) 6] 6+ macrocycle hosts CF3SO3 - anions, 4,4′-bipy and acetonitrile molecules. ► The skeletons of silver(I)–dppb complexes are affected by the nitrogen heterocyclic ligands and the solvent. ► 12 exhibit strong fluorescence emission peaks at room temperature. ► The 31P NMR spectra of 1or 2 shows that the P atoms coordinated to the center Ag atom have different chemical environment.
Keywords: Silver (I) complex; 14-membered ring; Network structure; Bis (diphenylphosphino) butane;

A novel metal-organic framework (MOF), namely, [Ag3(tptz)3(Mo5O17)](H3O)(H2O)1.5 (1), where tptz = 2,4,6-tri(4-pyridyl)-1,3,5-triazine, has been prepared under hydrothermal condition. Compound 1 is a chiral three-fold interpenetrated 3D MOF, in which the [Mo5O17]4 − anions act as templates, encapsulated in the chiral channels of the 3D framework.A novel 3D POM-templated three-fold interpenetrating MOF based on the rigid 2,4,6-tri(4-pyridyl)-1,3,5-triazine ligand has been successfully synthesized, where the optical band gap and the photoluminescent property have also been investigated.Display Omitted► We synthesized an exceedingly rare case of interpenetrating networks with polyoxometalates as templates. ► We investigated the conductivity of the compound. ► We studied the photoluminescent property of the compound. ► The compound is chiral. ► The [Mo5O17]4 − anion in the compound is rare.
Keywords: Metal-organic framework; Polyoxometalate-templated; Three-fold interpenetrated; Chirality;

Two dianionic amine bis(thiolato) ligands are introduced and their reactions with titanium tetra(iso-propoxide) studied; ligand N2H2S2 ―H2 (1) having NH donor groups leads exclusively to dinuclear [{Ti(N2H2S2)(O i Pr)}2] (2) along with an oxidation product of the ligand (3) whereas ligand N2Me2S2 ―H2 (4) having an additional N-substituent leads exclusively to a mononuclear [Ti(N2Me2S2)(O i Pr)2)] (5) type complex.Two dianionic amine bis(thiolato) ligands are introduced and their reactions with titanium tetra(iso-propoxide) studied. Ligand N2H2S2-H2 (1) having NH donor groups leads to dinuclear [{Ti(N2H2S2)(OiPr)}2] (2) along with an oxidation product “of the ligand (3) whereas ligand N2Me2S2-H2 (4) having an additional N-substituent leads to a mononuclear [Ti(N2Me2S2)(OiPr)2] (5) type complex. Display Omitted► Synthesis of new titanium complexes containing mixed NS-ligands. ► Effect of steric bulk on coordination features. ► Oxidation of thiolates to disulfides using titanium (IV).
Keywords: Titanium complexes; Structure; Bis-thiolato complexes; Amide coordination; Thiolate oxidation; Hydrolysis;

A new organic–inorganic hybrid zinc borate [Zn(dab)0.5(dab′)0.5(B4O6(OH)2)]·H2O has been hydrothermally synthesized by using 1,4-diaminobutane (dab) as the linkers and characterized by means of elemental analysis, IR spectroscopy, thermogravimetric analysis and single-crystal X-ray diffraction, respectively. This compound crystallizes in the monoclinic space group P21/c, a  = 9.997(3) Å, b  = 8.371(3) Å, c  = 16.321(4) Å, β  = 111.7(1)°, V  = 1268.8(7) Å3, Z  = 4. The structure contains ZnO2N2 tetrahedra, 1,4-dab and B4O7(OH)2 clusters, which interconnect to form a new three-dimensional framework.A new organic–inorganic hybrid zinc borate [Zn(dab)0.5(dab′)0.5(B4O6(OH)2)]·H2O has been made under hydrothermal conditions. In the structure, the B4O7(OH)2 cluster units are linked each other to produce a 1-D helical chain and further linked by the Zn2(dab) bridges to form a 2-D layer, which are further connected by another dab′ linkers, resulting in a 3-D open-framework.Display Omitted► A new organic–inorganic hybrid zinc borate [{Zn(dab)0.5(dab′)0.5}{B4O8H2}]·H2O has been hydrothermally made. ► It contains ZnO2N2 tetrahedra, dab and B4O7(OH)2 clusters, which links to form a new 3-D framework. ► It represents the first example of zinc borate expanding from 1-D to 2-D/3-D linked through organic amine molecules.
Keywords: Zinc borate; Hydrothermal synthesis; Template; Open-framework;

Anticancer activity of novel ruthenium complex with 1,10-phenanthrolineselenazole as potent telomeric G-quadruplex inhibitor by Qian Li; Dongdong Sun; Yanhui Zhou; Du Liu; Qianling Zhang; Jie Liu (142-146).
A novel Ru(II)–selenium complex [Ru(phen)2L](ClO4)2 (phen = 1,10-phenanthroline, L = 1,10-phenanthrolineselenazole) has been synthesized and structurally characterized by elemental analysis, ESI-MS and 1H NMR spectra, and the interaction between human telomeric G-quadruplex DNA (HTG21) and the new compound has been studied by emission spectra, visual detection assay, circular dichroism (CD) spectroscopy and fluorescence resonance energy transfer (FRET) melting assay. The results show that the complex has interaction with human telomeric G-quadruplex DNA which is visually detected, meanwhile it induces the guanine-rich single-strand oligomer d[G3(T2AG3)3] to form antiparallel G-quadruplex and has a moderate ability to stabilize G-quadruplex structures (ΔT m  = 11.2 °C). Furthermore, polymerase chain reaction-stop assay, telomerase repeat amplification protocol, and MTT assay demonstrate that the Ru-complex can exhibit well inhibitory activity for telomerase and cancer cells. The results suggest that Ru-complex may be a potential telomerase inhibitor for cancer chemotherapy.The scheme is the structure of the Ru-complex and its activity in PCR-stop assay.Display Omitted► This is the first report demonstrating that a novel ruthenium complex with selenium binding to G-quadruplexes. ► The Ru-complex induces the oligomer d[G3(T2AG3)3] to form and stabilize antiparallel G-quadruplex. ► TRAP assay demonstrate that the novel Ru-complex can exhibit well inhibitory activity for telomerase and cancer cells.
Keywords: Ru(II)–selenium complex; Spectral property; G-quadruplex; Telomerase; Anticancer activity;

A dinuclear oxomolybdenum(VI) complex, [Mo2O6(4,4′-di-tert-butyl-2,2′-bipyridine)2], displaying the {MoO2(μ-O)2MoO2}0 core, and its use as a catalyst in olefin epoxidation by Tatiana R. Amarante; Patrícia Neves; Filipe A. Almeida Paz; Martyn Pillinger; Anabela A. Valente; Isabel S. Gonçalves (147-152).
The dinuclear complex [Mo2O6(di-tBu-bipy)2] (1) (di-tBu-bipy = 4,4′-di-tert-butyl-2,2′-bipyridine) was obtained as a minor product of the hydrothermal reaction of MoO3 and di-tBu-bipy, and structurally characterized by single-crystal X-ray diffraction. In the molecular structure of 1 two distorted MoO6 octahedra share a common edge to form a dioxo-bridged Mo2O6 unit which is coordinated by di-tBu-bipy ligands. The catalytic performance of 1 for the epoxidation of non-functionalized olefins using tert-butylhydroperoxide as oxidant compares favorably with that reported for other oxomolybdenum(VI) complexes bearing the same organic ligand. The catalyst exhibits regioselectivity toward internal olefin epoxidation over external olefin epoxidation.A rare example of a dinuclear molybdenum complex exhibiting the {Mo2O6}0 core has been isolated from the hydrothermal reaction of MoO3 and 4,4′-di-tert-butyl-2,2′-bipyridine, and structurally characterized by single crystal X-ray diffraction. The complex is a particularly active and regioselective catalyst for the epoxidation of non-functionalized olefins using tert-butylhydroperoxide as oxidant.Display Omitted► The structure of a rare example of a dinuclear molybdenum complex exhibiting the {Mo2O6}0 core is described. ► Crystals of the complex were obtained after the hydrothermal reaction of MoO3 and 4,4′-di-tert-butyl-2,2′-bipyridine. ► The dioxo-bridged complex possesses catalytic activity for the epoxidation of non-functionalized olefins. ► The catalytic reaction is regioselective toward the epoxidation of internal double bonds.
Keywords: Molybdenum; Dinuclear complexes; 4,4′-di-tert-butyl-2,2′-bipyridine; Olefin epoxidation; Crystal structure;

Bisodium-substituted vanadium oxide cluster with encapsulated [VO4]4− core and its electrochemical property by Lili Zhang; Hengchao Zhang; Weisong Zhang; Hailiang Hu; Yang Liu; Zhenhui Kang (153-156).
A new hybrid compound [Cu(en)2]4[Na2VV 14VIV 2O42(VIVO4)]·2H2O (1) (en = ethylenediamine) has been hydrothermally synthesized. Single-crystal structural analysis indicates that compound 1 contains a novel bisodium-substituted [Na2V16O42(VO4)]8− cluster (abbreviated as Na2V16) with an encapsulated [VO4]4− core. The Na2V16 cluster exhibits a eight-connected model by providing eight terminal O atoms to link eight [Cu(en)2]2+ units, generating a three-dimensional (3D) network with 412·63 topology. Furthermore, the electrochemical property of 1 has been studied.A new 3D framework with an 6-connected topology based on a novel bisodium-substituted [Na2V16O42(VO4)]8− cluster encapsulated with [VO4]4− core has been successfully isolated and structurally characterized.Display Omitted► Novel bisubstituted [Na2V16O42(VO4)]8− cluster encapsulated with [VO4]4− core. ► The important role of big and highly charged [SO4]4− and [PO4]3− anions. ► The uncommon CV behavior of the title compound.
Keywords: Polyoxovanadates; Bisodium-substituted; Highly charged metal core; Electrochemical property;

A new type of polythreaded network self-assembled from sidearm-containing 2D bilayer motifs based on tetracarboxylate and N-heterocyclic multipyridyl ligand by Hai-Yan Chen; Dong-Rong Xiao; Juan Yang; Shi-Wei Yan; Jiang-Hong He; Xin Wang; Zhong-Li Ye; En-Bo Wang (157-161).
Hydrothermal reaction of zinc salt with 1,2,4,5-benzenetetracarboxylic acid (H4btec) and 2,4,5-tri(4-pyridyl)-imidazole (Htpim) in the presence of NaOH affords a new entangled metal–organic polymer [Zn2(btec)(Htpim)2]·2H2O (1). Compound 1 displays a new (2D → 3D) polythreaded network that is obtained for the first time from the self-assembly from 2D bilayer frameworks with dangling lateral arms, in which each large rectangular cavity of one bilayer is threaded by two dangling lateral arms of two adjacent bilayers coming from two opposite directions. The photoluminescence of 1 is also discussed.A new (2D → 3D) polythreaded network, that is obtained for the first time from the self-assembly from 2D bilayer frameworks with dangling lateral arms, is reported, which also defines a trinodal (3,4,6)-connected 3D self-threading network if H-bonds are taken into account.Display Omitted► Compound 1 represents the first (2D → 3D) polythreaded array assembled by infinite sidearm-containing 2D bilayer frameworks. ► Compound 1 also defines a trinodal (3,4,6)-connected 3D self-threading network if H-bonds are taken into account. ► Compound 1 displays good fluorescent property.
Keywords: Entangled network; Polythreaded network; Photoluminescent;

Reactions of the sodium salts of PhC(S)NHP(Y)(OiPr)2 (Y=S, HL I ; O, HL II ) with PPh4Br in 96% aqueous EtOH leads to the corresponding compounds PPh 4 L I,II . The structures of these compounds were investigated by IR, 1H, 31P{1H} NMR spectroscopies; their compositions were examined by microanalysis. Recrystallization of PPh 4 L I,II from EtOH/H2O solution (1:1, v/v) leads to the formation of HL II and PhC(O)NHP(O)(OiPr)2 (HL III ), respectively. The crystal structures of HL II,III are reported and compared with the previously reported polymorphs.Reactions of the sodium salts of PhC(S)NHP(Y)(OiPr)2 (Y=S, HL I ; O, HL II ) with PPh4Br give the corresponding compounds PPh 4 L I,II . Recrystallization of PPh 4 L I,II from EtOH/H2O solution leads to the formation of HL II and PhC(O)NHP(O)(OiPr)2 (HL III ), respectively. The crystal structures of HL II,III are reported and compared with the previously reported polymorphs.Display Omitted► Tetraphenylphosphonium salts of PhC(S)NHP(Y)(OiPr)2 (Y=S, O) are reported. ► The compounds were examined by IR, 1H and 31P{1H} NMR spectroscopy. ► New crystal polymorphs of PhC(X)NHP(O)(OiPr)2 (X=S, O) were obtained.
Keywords: Crystal structure; ES mass spectrometry; (Thio)phosphoryl(thio)benzamide; Tetraphenylphosphonium salt; H-bond networks; Polymorphism;

Efficient nuclease activity of dinuclear iron(III) complex with ligand having carboxamido nitrogen donors by Kaushik Ghosh; Nidhi Tyagi; Pramod Kumar; Sweety Rathi; Udai P. Singh (167-171).
A new dinucleating ligand N,N′-diphenyl-N,N′-di(pyridin-2-yl)oxalohydrazide (GampH2) has been synthesized and GampH2 gave rise to complex [Fe2(Gamp)(DMF)2Cl4], 1 with FeCl3 salt and 1 was isolated as shiny blue crystalline solid. The molecular structure of complex 1 was characterized by X-ray crystallography. In this dinuclear complex, Fe–Fe separation was found to be 5.49 Å and variable temperature magnetic moment was examined. Electrochemical investigation afforded a quasireversible redox couple with E1/2 value of 0.144 V vs Ag/AgCl. Complex 1 was efficient in DNA cleavage activity and enhancement of DNA cleavage was observed in the presence of 2-mercaptoethanol and hydrogen peroxide. Investigation of mechanism indicated possible involvement of hydroxyl radical in nuclease activity.A novel dinuclear iron(III) complex was synthesized and its structure was determined by X-ray crystallography. The complex itself exhibited DNA cleavage at high concentration; however, the efficiency was increased with the increase in incubation time and enhancement of nuclease activity was observed in presence of H2O2 and BME.Display Omitted► A dinuclear iron complex was synthesized and characterized by spectroscopic studies. ► Molecular structure of the complex was determined by X-ray crystallography. ► Nuclease activity was investigated.
Keywords: Dinucleating ligand; Dinuclear iron(III) complex; Carboxamido nitrogen; X-ray structure; Nuclease activity;

A new MnIV dinuclear complex [MnIV 2(μ-O)2(L′)4].2CH3OH (HL′ = (E)-N′-(1-(thiophen-2-yl)ethylidene)benzohydrazide) was obtained from MnIII(acetate)3.2H2O by an unusual MnIII disproportionation reaction. This compound exhibits a strong antiferromagnetic coupling with a J value of − 149(5) cm− 1. Moreover, a new MnIII mononuclear complex bearing L′ named [MnIII(acac)(L′)2] (acac = acetylacetonate) was obtained from [MnIII(acac)3] and is described as a part of a systematic research work around manganese complexes of magnetic interest.New Mn(IV) dinuclear complex [Mn(IV)2(μ-O)2(L′)4] (2) (HL′ = (E)-N′-(1-(thiophen-2-yl)ethylidene)benzohydrazide) – with strong antiferromagnetic coupling with a J value of approximately − 150 cm− 1 – spontaneously obtained by unusual Mn(III) disproportionation reaction.Display Omitted
Keywords: Manganese; Disproportionation; N′-(1-(thiophen-2-yl)ethylidene)benzohydrazide; Molecular magnetism;

A mixed donor macrocyclic ferrocenophane, 1,13-diselena-5,9-dithia[13]ferrocenophane (L), was synthesized. Reaction of L with [M(NCMe)4](PF6)2 (M = Pd, Pt) led to complexes [ML](PF6)2 (M = Pd, Pt). The structures of two complexes have been determined by X-ray crystallography. Cyclic voltammetry shows that, in [ML](PF6)2 (M = Pd, Pt), the half-wave potential of the 1,1′-ferrocenediyl group shifts to much more positive potentials due to the strong through-space interaction between the two metals (Fe…M) and sulfur atoms.A mixed donor macrocyclic ferrocenophane 1,13-diselena-5,9-dithia[13]ferrocenophane (L) and its complexes [ML](PF6)2 (M = Pd, Pt) have been synthesized. The structures of two complexes were determined. Cyclic voltammetry shows that the oxidation of the ferrocenyl group shifts much more positively after complexation.Display Omitted► Macrocyclic ferrocenophane 1,13-diselena-5,9-dithia[13]-ferrocenophane was prepared. ► The solid state structures of Pd(II), Pt(II) complexes adopt the c,t,c configuration. ► Sulfur atoms induces more positive shift of ferrocene oxidation after complexation.
Keywords: 1,13-Diselena-5,9-dithia[13]ferrocenophane; Crystal structure; Electrochemistry;

[Fe(4′-PhStpy)2][PF6]2 (4′-PhStpy = 4′-phenylthio-2,2′:6′,2″-terpyridine): A centrosymmetric embrace by Yaqiu Tao; Edwin C. Constable; Catherine E. Housecroft; Markus Neuburger (180-183).
The syntheses and characterizations of 4′-phenylthio-2,2′:6′,2″-terpyridine (4′-PhStpy) and [Fe(4′-PhStpy)2][PF6]2 are reported. In the solid state, centrosymmetric pairs of [Fe(4′-PhStpy)2]2 + cations in [Fe(4′-PhStpy)2][PF6]2·2MeCN associate through face-to-face π-stacking of pyridine rings, and twisting of the PhS substituents enables the cations to embrace one another, capturing four MeCN solvate molecules within the {Fe(4′-PhStpy)2}2-motif.Assembly of centrosymmetric pairs of [Fe(4′-PhStpy)2]2 + cations (4′-PhStpy = 4′-phenylthio-2,2′:6′,2″-terpyridine) results in a {Fe(4′-PhStpy)2}2-host that captures four MeCN molecules in [Fe(4′-PhStpy)2][PF6]2·2MeCN.Display Omitted► 4′-Phenylthio-2,2′:6′,2″-terpyridine (4′-PhStpy) ligand. ► Crystal structures of 4′-PhStpy and [Fe(4′-PhStpy)2][PF6]2. ► Centrosymmetric embrace of [Fe(4′-PhStpy)2]2 + cations. ► Host–guest interactions.
Keywords: 4′-Phenylthio-2,2′:6′,2″-terpyridine; Crystal structure; Iron; Host–guest;

Solvothermal reaction of Ni(OAc)2 with the new ligand 1,2-di(pyridin-2-yl)ethanone (HL) in the presence of NH4SCN in DMF/CH3OH solution affords a novel trinuclear Ni2+ complex [Ni3(L)2(OAc)2(SCN)2(DMF)2](DMF)1.5(H2O) (1). Crystal structure determination of 1 reveals a non-collinear Ni3-pattern bridged by the μ 2-Oenolate atoms of L and μ 3-acetate anions, which has rarely been found for trinuclear Ni2+ systems. Moderate ferromagnetic exchange was observed between the Ni2+ centers.This work presents the synthesis, crystal structure, and magnetism of a novel trinuclear Ni2+ complex with 1,2-di(pyridin-2-yl)ethanone (HL), in which the non-collinear Ni3-core is bridged by both μ2 -Oenolate of L and μ 3-acetate anions, exhibiting overall ferromagnetic interactions between Ni2+ centers.Display Omitted► A non-collinear [Ni2+]3 complex linked by μ2 -Oenolate and μ 3-acetate has been reported. ► 1,2-Di(pyridin-2-yl)ethanone tends to the enolate form in the complex. ► All interactions between Ni2+centers are ferromagnetic.
Keywords: Trinuclear nickel(II) complex; 1,2-Di(pyridin-2-yl)ethanone; Keto-enol tautomerism; Ferromagnetic coupling; O-enolate and acetate bridges;

Synthesis, structure and luminescence of new dinuclear cyanido-bridged AgI–AuI one-dimensional coordination polymer by Mohamed Ghazzali; Mohammed H. Jaafar; Khalid Al-Farhan; Sebastiaan Akerboom; Jan Reedijk (188-190).
A new alternating chain compound consisting of gold(I) and silver(I) bridged by cyanides is reported. The Ag(I) ion is functionalized by 2 triphenyl phosphane ligands, resulting in the formula [Au(CN)2(PPh3)2Ag]n. The compound has been prepared by room temperature reaction of triphenyl phosphane with the cyanide salts of silver(I) and gold(I). The product has been characterized and its single crystal X-ray structure was determined. In the molecular structure of the complex, the Au(I) centers exhibit the expected linear, two-coordinate geometry with C-bound cyanides, whereas the Ag(I) centers adopt a tetrahedral geometry in a AgN2P2 chromophore. The shortest hetero intermetallic separation distance is 4.94(7) Å. No aurophilic interactions are observed, but only the non-conventional C―H…Au hydrogen interactions are present. Upon excitation at 325 nm, a quite intense luminescence at 475 nm, assigned on the basis of DFT calculations to MMLCT, is observed, which amounts to ca. 10% of the luminescence intensity of the best known luminescent compounds.The AgI-AuI compound of formula [Au(C≡N)2(PPh3)2Ag]n for one-dimensional coordination polymer exhibits luminescence around 475 nm, by excitation at 325 nm.Display Omitted► New AgI–AuI dinuclear cyanido-bridged chain compound has been prepared. ► One-dimensional zig-zag like coordination polymer along the crystallographic c-axis. ► Exciting the title compound at 325 nm results in luminescence around 475 nm in a high yield.
Keywords: Bimetallic; Single-crystal X-ray diffraction; One-dimensional coordination polymer; Ag(I)–Au(I) complex; Luminescence; DFT;

The hydrothermal reactions of Keggin-type silicotungstate with rare-earth–transition-metal (RE–TM) heterometals in the presence of mixed ligands of oxalate and en (en = ethylenediamine) generate a novel two-dimensional (2D) organic–inorganic hybrid oxalate-bridging scandium-substituted silicotungstate. The complex [Cu(en)2(H2O)]2{[Cu(en)2(H2O)]2[Cu(en)2]2[(α-SiW11O39)Sc(H2O)]2(C2O4)}·8H2O (1) has been further characterized by elemental analyses, powder X-ray diffraction (PXRD), IR spectra, thermogravimetric (TG) analyses, and single-crystal X-ray diffraction. X-ray structural analysis reveals that 1 exhibits the dimeric mono-Sc substituted Keggin [Sc(α-SiW11O39)]2 10 − subunits linked by the oxalate ligand, which further results in the 2D network architecture interconnected by [Cu(en)2]2 + coordination cations. Notably, 1 represents the first oxalate-bridging RE–TM heterometallic hybrid built by lacunary Keggin silicotungstate-supported RE derivatives and [Cu(en)2]2 + coordination cations. Furthermore, the TG curve of 1 displays two steps of slow weight loss in the range of 25–1000 °C.The first two-dimensional organic–inorganic hybrid derivative constructed by oxalate-bridging scandium-substituted Keggin-type silicotungstate and [Cu(en)2]2 + coordination cations has been synthesized.Display Omitted► The first oxalate-bridging scandium-substituted Keggin-type silicotungstate. ► The first organic-inorganic hybrid 2D RE-TM heterometallic silicotungstate with the mixed organic ligands. ► The oxalate ligand acts as the tetradentate mode to bind two ScIII cations and two CuII ions, which has not been known.
Keywords: Keggin-type; Polyoxometalate; Silicotungstate; RE–TM heterometals; Oxalate;

Extended structure constructed from organic ligands functionalized sandwich-type tungstoferrates by Zhi-Shu Wang; Zhi-Ming Zhang; Xin-Bao Han; Huan Zhang; En-Bo Wang (196-200).
Two new compounds constructed from mixture-valence {Fe6}-cluster-containing sandwich-type tungstoferrates functionalized by N-donor ligands, (H2enMe)5{FeIII 2FeII 2(HenMe)2[B-α-FeW9O34]2}∙12H2O (1) and (H2enMe)3FeII(enMe)2H2{FeIII 2FeII 2 (HenMe)2[B-α-FeIIIW9O34]2}∙13H2O (2) (enMe = 1,2-diaminopropane) have been synthesized under hydrothermal conditions. Compound 1 is an isolated {Fe6}-cluster-containing sandwich-type tungstoferrate functionalized by two enMe ligands. Compound 2 exhibits a 1-D chain-like structure composed of the sandwich-type polyoxoanions linked by iron linkers via the bridging oxygen atoms, representing the first extended structure based on tungstoferrates. Also, the sandwich-type polyoxoanions coordinating with the transition-metal (TM) linkers with the bridging oxygen atoms is rarely observed in the polyoxometalate (POM) chemistry.A mixture-valence {Fe6}-cluster-containing sandwich-type tungstoferrate functionalized by two N-donor ligands has been synthesized under hydrothermal method, and the sandwich tungstoferrates are further linked by iron linkers via the bridging oxygen atoms into a 1-D chain-like structure.Display Omitted► Compounds 1 and 2 are both based on the mixture-valence {Fe6}-cluster-containing sandwich-type tungstoferrates. ► The sandwich structures in these two compounds are both functionalized by two N-donor ligands. ► Compound 2 represents the first extended structure based on tungstoferrates.
Keywords: Polyoxometalate; Tungstoferrate; Sandwich-type; Extended structure;

Construction of three lanthanide organic frameworks with (3,5)-connected topology based on 2-methyl-4,5-imidazoledicarboxylate and oxalate by Tianliang Ma; Jian Zhang; Xuemin Jing; Quan Feng; Bing Zheng; Yang Yu; Qisheng Huo; Yunling Liu (201-204).
Three novel 3D lanthanide organic frameworks [Ln2(H2O)3(HMImDC)2(OX)]·4H2O (Ln = Sm(1), Eu(2) and Gd(3), H3MImDC = 2-methyl-4,5-imidazoledicarboxylic acid, OX = oxalic acid) have been solvothermally synthesized and structurally characterized by elemental analyses, Infrared spectra (IR), thermogravimetric analyses (TGA), powder X-ray diffractions (PXRD), and single-crystal X-ray diffractions. Compounds 13 are isostructural and exhibit novel 3D architectures with open channels viewed along the a axis, which constructed from [Ln(HMImDC)(OX)] layers and Ln2(HMImDC)2 dimers. The framework of 13 can be rationalized as a (3, 5)-connected net with a unique (4.5.7)2(5.6.7)(52.63.7.83.10) topology. The luminescence and magnetic properties are also investigated.Structural views of the three three-dimensional coordination polymers [Ln2(H2O)3(HMImDC)2(OX)]·4H2O (Ln = Sm(1), Eu(2) and Gd(3)). In the structure, the lanthanide ions coordinate with 2-methyl-4,5-imidazoledicarboxylate and oxalic acid mixed ligands to give a 2D layer, which is further connected by the Ln2(HMImDC)2 dimers to construct 3D frameworks with (3,5)-connected network.Display Omitted► Lanthanide organic frameworks based on 2-methyl-4,5-imidazoledicarboxylate and oxalic acid mixed ligands. ► Compounds 13 have (3, 5)-connected networks. ► Compound 2 exhibits strong red luminescence emission. ► Compound 3 shows weak antiferromagnetic interactions.
Keywords: Lanthanide organic frameworks; 2-methyl-4,5-imidazoledicarboxylate; Crystal structure; Luminescence; Magnetism;

Unusual 3D pillared-layer Pb(II) complex supported by mercapto-triazole ligand: Synthesis, structure and luminescent property by Jingjing Zhao; Linke Li; Changhong Wang; Wenju Li; Ruina Wang; Xiaofang Zheng; Hongwei Hou (205-208).
Reaction of 4-amino-3-(4-pyridyl)-5-mercapto-1,2,4-triazole (a-Hptt) with PbCl2 hydrothermally has yielded complex [PbCl(ptt)]n (1) at pH 5. And the ligand a-Hptt can be deaminated and transformed into Hptt under hydrothermal condition (pH 5). The structure of 1 has been fully characterized by single crystal X-ray diffraction, elemental analysis, IR, as well as luminescent property. Structural analysis reveals that complex 1 is constructed from 2D two-component layers, which alternately arrange in the ⋯ABAB⋯ pattern, and then further pillared by Hptt ligands into an interesting 3D “pillared-layer” architecture. Complex 1 also shows strong luminescence emission in solid state at room temperature and may be suitable as a candidate for potentially photoactive material.Unusual 3D pillared-layer Pb(II) complex with a (4,8)-connected topology of (32·48·512·62·74)(32·45·53) has been prepared by 4-amino-3-(4-pyridyl)-5-mercapto − 1,2,4-triazole (a-Hptt) under hydrothermal condition. Structural analysis of 1 reveals that a-Hptt can be deaminated and transformed into Hptt at pH 5. 1 also shows strong luminescence emission in solid state at room temperature.Display Omitted► Unusual 3D pillared-layer Pb(II) complex 1 has been obtained by a-Hptt under hydrothermal condition. ► Structural analysis of 1 shows that a-Hptt can be deaminated and transformed into Hptt at pH 5. ► This work provides a potential photoactive material with strong luminescence emission in solid state.
Keywords: Lead(II) complex; Crystal structure; Mercapto-triazole ligand; Luminescent property;

Rare monomeric as well as dimeric Cu(II) complexes, [Cu2(β-pic)4L4][Cu(β-pic)2L2(H2O)2]·2H2O (1), (where L = cinnamate and β-pic = β-picoline) in one single crystal have been synthesized by the reaction of copper(II) cinnamate and excess of β-pic while a monomeric complex [Cu(py)2L2(H2O)]·py (2) was obtained in a similar reaction by using py (py = pyridine) instead of β-pic. Both of these copper(II) complexes have been characterized by spectroscopic techniques, TGA, X-ray crystallography and DFT studies.A rare monomeric–dimeric copper(II) complex.Two copper(II) cinnamate complexes, [Cu2(β-pic)4L4][Cu(β-pic)2L2(H2O)2]·2H2O, 1 and [Cu(py)2L2(H2O)]·py 2 (where L = cinnamate) has been synthesized, characterized by spectroscopic techniques, TGA and X-ray crystallography and supported by DFT calculations. Complex 1 represents rare monomer–dimer units in a single crystal.Display Omitted► Synthesis of two copper(II) cinnamate complexes have been described. ► Complexes were characterized by spectroscopy, X-ray crystallography and DFT studies. ► One of the complex represents rare monomer–dimer units in a single crystal.
Keywords: Copper(II) complex; Monomer–dimer; X-ray crystallography; DFT studies; EPR;

pH Dependent structural diversity of lead compounds based on new flexible ligand [3-(2-pyridyl)-1-pyrazolyl] acetic acid by Qiao-Yun Li; Ming-Hua He; Zhen-Dong Shen; Gao-Wen Yang; Zhi-Yong Yuan (214-218).
Two new Pb(II)/pypza compounds, namely, [Pb3(pypza)2Cl4] (1) and [Pb(pypza)Cl](2) (Hpypza = [3-(2-pyridyl)-1-pyrazolyl] acetic acid), have been synthesized through a hydrothermal method under different pH conditions, and characterized by single-crystal X-ray diffraction, element analysis, infrared spectra (IR). Compound 1 shows an unusual one-dimensional structure while compound 2 displays a novel two-dimensional network framework. Furthermore, the luminescence properties of 1 and 2 were investigated at room temperature in the solid state.Two new Pb(II)/pypza compounds, [Pb3(pypza)2Cl4] (1) and [Pb(pypza)Cl](2) (Hpypza = 3-(2-pyridyl)-1-pyrazolyl acetic acid ), have been synthesized through a hydrothermal method under different pH conditions. The luminescence properties of 1 and 2 were investigated at room temperature in the solid state.Display Omitted► Two Pb(II)/pypza metal-organic frameworks were synthesized. ► [3-(2-pyridyl)-1-pyrazolyl] acetic acid(Hpypza) ligand were studied. ► The luminescence properties of two complexes were investigated.
Keywords: Pb(II); [3-(2-pyridyl)-1-pyrazolyl] acetic acid; Crystal structure; Luminescence;

[Ni(dmit)2] salt with flexible supramolecular cation rotator by Qiong Ye; Ping-Ping Shi; Zi-Qi Chen; Tomoyuki Akutagawa; Shin-ichiro Noro; Takayoshi Nakamura (219-224).
[Ni(dmit)2] salt (dmit2  2-thioxo-1,3-dithiole-4,5-dithiolate) with flexible supramolecular cation (4-cyanomethylanilinium)(dibenzo[18]crown-6) has been synthesized and investigated its structure, magnetism and rotation. The comparable large steric hindrances limit the rotation of cyanomethyl group to result in no phase transition occurred. Magnetic and potential energy calculations by DFT method were consistent with the magnetic and structure measurements.[Ni(dmit)2] salt (dmit2  = 2-thioxo-1,3-dithiole-4,5-dithiolate) with flexible supramolecular cation (4-cyanomethylanilinium)(dibenzo[18]crown-6) have been synthesized and investigated its structure, magnetism and rotation. The comparable large steric hindrances limit the rotation of cyanomethyl group to result in no phase transition occurred. Magnetic and potential energy calculations by DFT method were consistent with magnetic and structure measurement results.Display Omitted► [Ni(dmit)2] salt (dmit 2  = 2-thioxo-1,3-dithiole-4,5-dithiolate) with flexible supramolecular cation (4-cyanomethylanilinium)(dibenzo[18]crown-6). ► Structure at low and room temperature have been measured and no phase transition happened. ► The comparable large steric hindrances calculated by DFT limit the rotation of cyanomethyl group to result in no phase transition occurred. ► Magnetism of the title compound shows antiferromagnetic interaction. ► Anionic interaction has been calculated by charge transfer integral and DFT method.
Keywords: Crystal engineering; Flexible; Molecular rotator; Supramolecule;

A facile method is demonstrated to obtain CeO2 by hydrolyzing coordination polymer nanowires Ce(1,3-BDC)1.5·6H2O (1,3-BDC = 1,3-benzene dicarboxylate) in basic solution. The products that preserved the morphologies of the precursors were constituted from plenty of CeO2 nanoparticles. This method can increase the surface areas significantly, which is important for its application in catalytic activities. Importantly, La (OH)3 nanoparticles could be obtained after the basic treatment of corresponding coordination polymer, indicating that this method is general to be applied to obtain other lanthanide oxides and hydroxides. After calcinations, well crystallized oxides exhibited different properties from their bulk counterparts due to their increased surface areas.CeO2 and La (OH)3 nanoparticles were obtained by hydrolyzing coordination polymers in basic solution at room temperature while still preserving the morphologies of their precursors.Display Omitted► CeO2 nanoparticles were obtained by hydrolyzing polymer in basic solution. ► The CeO2 with high surface areas preserved the morphologies of the precursors. ► The products show different properties from their bulk counterparts. ► This method can be applied to other lanthanide polymers.
Keywords: Nanoparticles; Polymeric composites; Phase transformation;

Solvothermal synthesis, structure and characterization of 1D chain and 2D layered rare earth sulfates in the presence of cyclic diamines by Gen-Wu Ge; Zhi-Yuan Qi; Zhi-Gang Ni; Yi-Zhi Li; Hong-Bin Du; Xiao-Zeng You (228-233).
Three new rare earth sulfates were solvothermally synthesized and characterized by X-ray diffraction, elemental analysis, thermogravimetric, and photoluminescent studies. Compounds [(NH4)(C6N2H12)][Ln(SO4)3] (Ln=Eu, 1; Gd, 2) were synthesized in the solvent of DMA with 1,4-diazabicyclo-[2,2,2]-octane (DABCO) as a structure-directing agent (SDA), which are isomorphous and adopt a two-dimensional layered structure with 8-membered rings made of LnO8 polyhedra and SO4 tetrahedra. The protonated DABCO molecules lie between the layers while the ammonium cations are located within the layers. Compound [(C4N2H12)1.5][Er(SO4)3(H2O)] (3) was synthesized in the mixed solvent of water and ethanol with piperazine (PIP) as a SDA. The structural analyses showed that 3 is constructed from ErO9 polyhedra and SO4 tetrahedra to form a one-dimensional chained structure with edge-sharing 4-membered rings. The protonated PIP molecules and coordination H2O molecules form extensive intra- and inter-chain hydrogen bonding to generate a 3-dimensional supramolecular network. The three compounds exhibit good thermal stability. Compound 1 exhibits intense red luminescence upon excitation owing to the Eu3+ ion.Three new rare earth sulfates were solvothermally prepared by using cyclic diamines as structure directing agents, which possess a 2D layered, and a 1D chain structure, respectively.Display Omitted►Three new rare earth sulfates were solvothermally synthesized by using cyclic diamines ►1 and 2 are isomorphous and adopt a two-dimensional layered structure with 8-membered rings ►3 possesses a one-dimensional chained structure with edge-sharing 4-membered rings. ►1 exhibits intense red luminescence upon excitation owing to the Eu3+ ion
Keywords: Sulfate; Rare earth; Structure; Synthesis; Photoluminescence;

Synthesis, structure, and catalytic activity of a new zinc complex derived from a chiral hydroxyazetidine ligand by Zhanbin Zhang; Ning Zhao; Wenshan Ren; Liang Chen; Haibin Song; Guofu Zi (234-237).
A new chiral tetrameric zinc complex [(1)ZnEt]4 (2) has been readily prepared via alkane elimination between ZnEt2 and a chiral azetidine derivative, (2R,3R)-1-[(1S)-1-(4-methoxyphenyl)ethyl]-2-phenyl-3-hydroxyazetidine (1H). Complex 2 has been characterized by various spectroscopic techniques, elemental analyses, and X-ray diffraction analysis. Complex 2 has a cubane-like Zn4O4 core structure, and is an active catalyst for the polymerization of rac-lactide, leading to the heterotactic-rich polylactides.A new chiral organozinc complex has been prepared and structurally characterized. It is an active catalyst for the polymerization of rac-lactide, leading to the heterotactic-rich polylactides.Display Omitted► A new chiral organozinc complex has been prepared and structurally characterized. ► Its structure has a cubane-like Zn4O4 core. ► It is an active catalyst for the polymerization of rac-lactide, leading to the heterotactic-rich polylactides.
Keywords: Chiral azetidine ligand; Zinc complex; Synthesis; Structure; Polymerization of lactide;

Chelating behavior and biocidal efficiency of tryptophan based mixed-ligand complexes by Muthusamy Selvaganapathy; Natarajan Raman (238-242).
A new family of tryptophan based mixed-ligand complexes has been synthesized and characterized. DNA (Calf thymus) binding properties of the complexes have been explored by UV–vis, viscosity measurements and cyclic voltammetry. All the experimental evidence suggest that the ancillary ligand 2,2′-bipyridine influences the intercalative binding of these complexes to CT DNA. The DNA cleavage efficiencies of these complexes with pBR322 DNA were investigated by gel electrophoresis. The complexes were found to promote the cleavage of pBR322 DNA from the supercoiled form I to the open circular form II in the presence of an oxidizing agent (H2O2). Microbial property of these complexes as antibacterial agents has been investigated against Gram-negative and Gram-positive bacteria.Tryptophan based mixed ligand complexes were synthesized and characterized. They can interact with DNA through an intercalative binding mode and exhibit good biocidal efficiency against different organisms.Display Omitted► Synthesis of a new family of tryptophan-derived mixed-ligand complexes. ► They were found to act as good intercalators and anti-bacterial agents. ► These chelates exhibit efficient cleavage potential of pBR322 DNA. ► To develop the novel design of new metallonucleases.
Keywords: Tryptophan-based mixed-ligand complexes; DNA binding; DNA cleavage; Microbial property;

A new mixed-azolate Cu(I)-framework based on dinuclear and tetranuclear clusters: Synthesis, structure and luminescence by Wen-Juan Shi; Lei Hou; Yao-Yu Wang; Lu-Lu Zhang; Li Zhao; Qi-Zhen Shi (243-246).
A new two-dimensional Cu(I)-framework [Cu3(deppz)(mtta)I] (1) [(Hdeppz = 3,5-diethyl-4-(4-pyridyl)-pyrazole, Hmtta = 5-methyltetrazole] has been solvothermally synthesized and structurally characterized. The framework contains an unprecedented cyclic Cu4(μ-pz)2(μ-mtta)2 cluster (Cu 4 ) with twelve-membered coplanar Cu4N8 metallocycle, which contains coordinatively unsaturated Cu(I) centers and acts as a soft π-acid motif to contact with iodine atoms from Cu2I2 dimer of adjacent layers, generating a 3D supramolecular framework. The framework exhibits high thermostability and bright green-blue solid-state luminescence.A new mixed-azolate Cu(I)-framework has been constructed by the assembly of dinuclear, tetranuclear clusters and 3,5-diethyl-4-(4-pyridyl)-pyrazole, 5-methyltetrazole ligands, which exhibits both high thermostability and strong photoluminescence.Display Omitted► A new Cu(I)-azolate framework possessing dinuclear and tetranuclear clusters. ► The framework contains coplanar tetramer π-acid···I interactions. ► The framework exhibits both high thermostability and green-blue luminescence.
Keywords: Metal-organic framework; Copper; Azolate; Crystal structure; Luminescence;

A series of lanthanide compounds based on mixed aromatic carboxylate ligands: Syntheses, crystal structures and luminescent properties by Xiang Zhao; Xiao-Yang Yu; Tian-Li Chen; Yu-Hui Luo; Jia-Jun Yang; Hong Zhang (247-251).
A series of lanthanide complexes, [LnL1L2 1/2(H2O)2]n [Ln = La(1), Sm(2), Gd(3), Eu(4), H2L1  = 2,4-bis(4-methylbenzoyl)isophthalic acid and H2L2  = 2,5-bis(4-methylbenzoyl)terephthalic acid] have been prepared under hydrothermal conditions and characterized by PXRD, IR, elemental analysis and single crystal X-ray diffraction. Complexes 14 are isostructural and comprise paddlewheel dinuclear lanthanide secondary building units linked by four carboxylic groups. L1 ligands link the dinuclear lanthanide building blocks to form one-dimensional double-stranded looplike chains. The chains are further connected together to form two-dimensional layers by L2. Furthermore, the luminescent properties of 2 and 4 were also studied.Four isostructural lanthanide compounds constructed with two different substituted aromatic carboxylate ligands have been prepared hydrothermally. 2,4-Bis(4-methylbenzoyl)isophthalic acids link the paddlewheel dinuclear units into 1D double-stranded looplike chains. And the chains are further connected into 2D layers by 2,5-bis(4-methylbenzoyl)terephthalic acids. The luminescent properties of 2 and 4 were also studied.Display Omitted► A series of lanthanide coordination polymers have been synthesized. ► The lanthanide compounds are constructed by two substituted aromatic carboxylate ligands. ► The photoluminescent properties have been investigated.
Keywords: Crystal structure; Lanthanide(III); Mixed aromatic carboxylate; Hydrothermal reaction; Luminescence;

A novel Ru(II) complex derived from hydroxydiamine as a potential antitumor agent: Synthesis and Structural Characterization by Mohammad Azam; Ismail Warad; Saud Al-Resayes; Mohammad Shakir; M.F. Ullah; Aamir Ahmad; Fazlul H. Sarkar (252-258).
A novel Ru(II)-Schiff base complex has been synthesized by the interaction of ligand, 1,3-bis{[(E)-(2-chlorophenyl)methylidene]amino}-2-propanol, L with [RuCl2(PPh3)3]. The structure of ligand, L has been determined on the basis of X-ray diffraction while the geometry of the Ru(II) complex has been ascertained by FT-IR, 1H, 13  C{1H}, 31P{1H} NMR and UV–vis studies. The in vitro antitumor activity of these compounds was assessed by examining their ability to inhibit cell proliferation against human breast and pancreatic cancer cell lines. The results show a dose-dependent anti-proliferative effect and induction of apoptotic cell death in both the cancer cell lines, thus indicating pharmacological significance of Ru(II) complex against cancer.A novel Schiff base ligand and its Ru(II) complex has been synthesized and characterized by various spectroscopic techniques followed by their screening to examine their ability to inhibit cell proliferation in a number of human cancer cell lines (MDA-MB-231) and (BxPC-3).Display Omitted► Synthesis of a novel Schiff base ligand and its Ru(II)-complex. ► Characterized by various physico-chemical and spectroscopic studies. ► In vitro antitumor screening proved them potent growth inhibitor.
Keywords: Ru(II) complex; 31P{1H}NMR; Anticancer activity;

Crystal structures of chiral mono- and dinuclear salan–Cu(II) complexes and the application to catalytic asymmetric Henry reaction by Yan Shi; Zhijie Mao; Qicai Xue; Chengjian Zhu; Hongwen Hu; Yixiang Cheng (259-262).
Two chiral salan–Cu(II) complexes, dinuclear {[(C28H26CuN2O2)2  · 2CH3OH∙CH3COOH] (1)} and mononuclear {[C56H55CuN4O4∙½CH3OH∙CH3COOH∙H2O] (2)} were synthesized and structurally characterized. The complex 1 was obtained with the ratio 1:1.2 of the metal source and the ligand, in which the two copper atoms were bridged by μ–O atoms forming a four-membered binuclear Cu2O2 square–planar geometry. However, using two equivalents of the ligand led to the formation of the complex 2, in which one copper atom coordinated with two salan ligands bound in a five-coordinate square–pyramidal. The asymmetric Henry reaction was studied by these in situ formed complexes. The complex 1 provided moderate to high enantioselectivities (up to 83%) when the reaction was carried out in EtOH at room temperature for 48 h, whereas the complex 2 gave a modest enantioselectivity.The complex 1 can be applied into asymmetric Henry reactionDisplay Omitted► We have prepared and structurally characterized two salan–copper complexes. ► Different ratio of metal and ligand leads to the two chiral copper complexes. ► By means of IR, CD and thermal analysis, the two complexes were studied. ► Both the complexes were tested for asymmetric Henry reaction, the highest ee is 83%.
Keywords: Crystal structures; Copper; Salan ligands; Asymmetric catalysis; Henry reaction;

A nanosized porous metal-organic framework assembled with mutually interdigitated two-dimensional coordination motifs by Hong-Qing Hao; Meng-Xia Peng; Lan Li; Shan-Ji Li; Xin-Rong Wen (263-265).
A metal-organic framework based on silver(I) and mixed ligands {[Ag2(ibpa)2(bpp)2]·5H2O}n (1) (Hibpa = 4-isobutyl-α-methylphenylacetic acid, bpp = 1,3-di(4-pyridyl)propane) has been synthesized by the solvothermal reaction. Single crystal X-ray diffraction revealed that 1 has a two-dimensional (2D) layer motif, and the layers of 1 are further mutually interdigitated to give rise to a 3D nanosized porous framework in the dimension of 13.23 × 13.19 Å. Interestingly, the host framework encapsulates unique hexamer water clusters and is further connected into (H2O) 6n tapes by water–water hydrogen bonding interactions. Thermogravimetric analysis (TGA) was conducted to determine the thermal stability of 1.A nanosized porous metal-organic framework constructed with an interesting flexible 2D interdigitated layer and encapsulating unique (H2O) 6n tapes based on hexamer water clusters.Display Omitted► Firstly, a nanosized porous metal-organic framework has been synthesized. ► Secondly, it is comprised of the mutually interdigitated 2D layer motifs. ► Thirdly, it encapsulates unique hexamer–water clusters. ► Fourthly, the water clusters are connected into (H2O) 6n tapes by hydrogen bonds.
Keywords: Porous metal-organic framework; Interdigitated motifs; Water cluster;

A new three-dimensional (3D) metal-organic framework [Cd2(Ad)2(IN)2(DMF) (H2O)]·DMF (1; Ad = Adenine; IN = isonicotinic acid) with unusual cadmium–adeninate “paddle-wheel” building block has been solvothermally synthesized and structurally characterized by single crystal X-ray diffraction, powder X-ray diffraction (PXRD), thermogravimetric analysis (TG) Elemental analysis (EA) and Infrared Spectroscopy (IR). Compound 1 exhibits 4-connected moganite (mog) topologic network.Presented here is a new MOF with 4-connected mog topology constructed from cadmium–adeninate paddle-wheel units.Display Omitted► A new adenine-based 3D Metal-organic framework. ► The observation of cadmium–adeninate “paddle-wheel” subunit. ► A 3D compound with 4-connected moganite (mog) topological network and two different Cadmium-organic chains.
Keywords: Metal-organic framework; Topology; SBUs; Paddle wheel;

Novel semiconducting metal-organic framework: Synthesis, structural characterisation and electrical conductivity studies of manganese based two dimensional coordination polymer by Muthuraman Karthikeyan; Bussa Bhagyaraju; Chinnasamy Ramaraj Mariappan; Shaikh M. Mobin; Balasubramanian Manimaran (269-272).
New Manganese(II) dichloro and pyrazine bridged coordination polymer containing rectangular framework [Mn(μ-pz)(μ-Cl)2]n was synthesised and structurally characterised. Single crystal X-ray structure of the coordination polymer [Mn(μ-pz)(μ-Cl)2]n displayed 2D rectangular framework with infinite sheet structure. Thermogravimetric analysis showed that the [Mn(μ-pz)(μ-Cl)2]n coordination polymer is stable and robust up to 310 °C. Electrical conductivity measurements of [Mn(μ-pz)(μ-Cl)2]n were carried out as a function of frequency at various temperatures and the coordination polymer exhibited semiconducting property with activation energy Ea  = 0.70 (± 0.03) eV.Manganese based coordination polymer [Mn(μ-pz)(μ-Cl)2]n has been synthesised and characterised. Single crystal X-ray structure reveals that the coordination polymer exhibits 2D sheet structure with rectangular framework. Electrical conductivity studies of this coordination polymer exhibited semiconducting behaviour with activation energy Ea  = 0.7 eV.Display Omitted► Novel two dimensional coordination polymer [Mn(μ-pz)(μ-Cl)2]n was synthesised. ► Manganese based metal-organic framework was structurally characterised. ► Crystal structure exhibited rectangular framework with infinite sheet structure. ► Conductivity study of coordination polymer displayed semiconducting behaviour. ► Thermogravimetric analysis revealed the robust nature of coordination polymer.
Keywords: Manganese; Pyrazine; Coordination polymer; Electrical conductivity; Semiconducting material.;

A new inorganic–organic hybrid compound constructed from Keggin-type polyoxometalate and cadmium-organic units, namely, [Cd(Htrz)3]2[SiW12O40]·2H2O (1), [Htrz = 1-H-1,2,4-triazole], has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction, IR, TG, and UV–vis absorption spectra. In compound 1, each [SiW12O40]4 − cluster is modified by six [Cd(Htrz)3]2 + metal–organic fragments, meanwhile, each [Cd(Htrz)3]2 + also connects with three [SiW12O40]4 − to built up a binodal (3,6)-connected 2D planar network with the (43)2(46·66·83)-kgd topology. Interestingly, [SiW12O40]4 − cluster exhibits a rare coordination mode acting as a hexadentate ligand, in which all of the six terminal oxygen atoms in the equatorial plane are synchronously participated in coordination. The diffuse reflectivity spectrum shows it can be regarded as a wide gap semiconductor. Moreover, the photocatalytic performance shows good photocatalytic activity for the degradation of Rhodamine B.Compound 1 constructed from Keggin-type polyoxometalate and cadmium-organic units, exhibits a binodal (3, 6)-connected 2D planar network with the (43)2(46·66·83)-kgd topology. The diffuse reflectivity spectrum shows 1 can be regarded as a wide gap semiconductor. The photocatalysis and electrochemical properties have been also investigated.Display Omitted► Compound 1 exhibits a binodal (3,6)-connected 2D planar framework. ► [SiW12O40]4 − furnishes the six terminal oxygen atoms in the equatorial plane to coordinate. ► 1 can be regarded as a wide gap semiconductor. ► 1 shows outstanding photocatalytic activity for the degradation of Rhodamine B.
Keywords: Inorganic–organic hybrid material; Hydrothermal synthesis; Polyoxometalate; Photocatalysis property;

Synthesis, structure and properties of a metal–organic complex built up from ferrous sulfate chains and 2,2'-bipyridyl-5,5'-dicarboxylic acid ligands by Dongying Shi; Suzhi Li; Junwei Zhao; Weijia Niu; Sensen Shang; Yanzhou Li; Pengtao Ma; Lijuan Chen (277-281).
A novel metal–organic complex [Fe(H2bpdc)]SO4 (1) has been hydrothermally synthesized (H2bpdc = 2,2'-bipyridyl-5,5'-dicarboxylic acid) and structurally characterized by elemental analyses, IR spectra, powder X-ray diffraction and single-crystal X-ray diffraction, which displays the first 1-D ferrous sulfate chain functionalized by H2bpdc. Interestingly, the 3-D supramolecular structure of 1 can be constructed by means of hydrogen-bonding interactions and Fe···O short contacts. Thermogravimetric analysis indicates that 1 shows a good thermal stability and can be thermally stable up to 420 °C. Magnetic measurements of 1 exhibit the existence of antiferromagentic interactions within the FeII centers.A novel metalorganic complex [Fe(H2bpdc)]SO4 has been hydrothermally synthesized (H2bpdc = 2,2'-bipyridyl-5,5'-dicarboxylic acid), which displays the first 1-D architecture constructed from ferrous sulfate chains and H2bpdc ligands.Display Omitted► the ferrous sulfate chain. ► 2,2'-bipyridyl-5,5'-dicarboxylic acid. ► metal–organic complex constructed from ferrous sulfate chains and H2bpdc ligands. ► the antiferromagentic interactions within the FeII centers.
Keywords: Metal–organic complex; Ferrous sulfate; 2,2'-bipyridyl-5,5'-dicarboxylic acid; Magnetism;

Direct synthesis and properties of monomeric and dimeric MnIII–salen complexes tuned by tetrahalocadmate anions by Eduard M. Chygorin; Valeriya G. Makhankova; Mykola V. Ischenko; Vladimir N. Kokozay; Roman I. Zubatyuk; Oleg V. Shishkin; Julia Jezierska (282-285).
Two novel compounds [Mn(salen)(dmf)2]3[Mn(salen)(dmf)(H2O)][CdCl4]2·H2O (1) and {[Mn(salen)(CH3OH)]2}[Mn(salen)(CH3OH)2]2[CdI4]2 (2) have been synthesised via interaction of manganese metal and cadmium halide with in situ generated salen ligand (salen =  N,N′-ethylene-bis-salicylideneaminato) in non-aqueous (dmf, CH3OH) solutions. X-ray structure analysis reveals that in solid state 1 contains mononuclear MnIII–salen species, whilst in 2 both monomeric and out-of-plane dimeric MnIII–salen complexes are present. Moreover, in 2 the monomeric units are linked by H-bonds, forming other dimers. Equilibrium between monomeric and dimeric units in solutions of 1 and 2 was found by ESI mass-spectrometry. The magnetic measurements of 2 demonstrated antiferromagnetic interactions between MnIII centres.The antiferromagnetic interactions between MnIII centres in out-of-plane dimers and H-bonded dimers are found in {[Mn(salen)(CH3OH)]2}[Mn(salen)(CH3OH)2]2[CdI4]2.Display Omitted► Two Mn–salen complexes with tetrahalocamates were synthesized. ► Equilibrium between monomeric and dimeric Mn–salen units in solutions is observed. ► Rare case of antiferromagnetic interactions between MnIII centres in dimers was found.
Keywords: Schiff base ligand; Cadmium; Manganese; X-ray crystallography; Antiferromagnetic interactions;

An alternating hexameric water (H2O)6 cluster and a chlorine-water cluster [Cl2(H2O)4]2- in the chair forms combine axially to each other to form a 1D chain [{Cl2(H2O)6}2−]n in complex [FeL2]Cl·(H2O)3 (L = 2-[(2-methylaminoethylimino)-methyl]-phenol)]. The water molecules display extensive H-bonding interactions with monomeric iron–organic units to form a hydrogen-bonded 2D supramolecular assembly.A 1D water-chloro anionic layer [{Cl2(H2O)6}2−]n in which alternating chair conformations of hexameric cyclic water clusters (H2O)6 and chlorinated water clusters [Cl2(H2O)4]2– are connected axially which is unprecedented as presumed to be energetically unfavourable.Display Omitted► Synthetic, structural and spectral study of the complex [FeL2]Cl•(H2O)3. ► An unusual water-chloro anionic chain, [{Cl2(H2O)6}2−]n is stabilized. ► The chain contains alternating (H2O)6 and [Cl2(H2O)4]2– in chair conformations. ► Two alternating chair conformations are connected axially.
Keywords: Hydrogen-bonded; Chlorine-water cluster; Chair conformation; X-ray diffraction analysis; Decahydronaphthalene;

Water helicate (H2O)5 hosted by a novel 2D CoII-coordination framework with left- and right-handed helical units by Geng-Geng Luo; Sheng-Hui Wu; Qing-Hua Zhao; Dong-Xu Li; Zi-Jing Xiao; Jing-Cao Dai (290-294).
A novel 2D cobalt(II) coordination polymer comprising left- and right-handed helical chains, {[H2bpp][Co2(bpp)2(Hbtec)2(H2O)4]·(H2O)5}n (1) (bpp = 1,3-bis(4-pyridyl)-propane and H4btec = 1,2,4,5-benzenetetracarboxylate), was prepared under hydrothermal conditions and characterized by single-crystal X-ray diffraction method. Complex 1 provides suitable hydrophilic channel in which lattice water molecules accumulate, forming a (H2O)5 helicate, stabilized by anchoring to the host structure through hydrogen-bonding interactions involving alternating water molecules and the carboxylate oxygen atoms of Hbtec3− ligands.A novel form of water aggregate, viz., (H2O)5 helicate, has been trapped in the hydrophilic channel of a novel 2D cobalt(II) coordination polymer comprising left- and right-handed helical chains {[H2bpp][Co2(bpp)2(Hbtec)2(H2O)4]·(H2O)5}n (1) (bpp = 1,3-bis(4-pyridyl)-propane and H4btec = 1,2,4,5-benzenetetracarboxylate).Display Omitted► One novel 2D cobalt(II) coordination polymer was synthesized and characterized. ► The coordination polymer comprises left- and right-handed helical chains. ► A novel water helicate (H2O)5 has been trapped in the hydrophilic channel of the coordination polymer.
Keywords: Coordination polymers; 1,2,4,5-benzenetetracarboxylate(H4btec); Helical chains; (H2O)5 helicate; Hydrogen bonds;

Hydrothermal syntheses and crystal structures of a series of 3d–4f heterometallic tetrazole-based coordination polymers by Li Liang; Guizhu Li; Lin Sun; Guoqiang Lan; Limin Zhang; Chengfeng Yang; Yingzhao Ma; Hong Deng (295-298).
A series of novel three-dimensional (3D) Ln(III)–Cu(I) heterometallic tetrazole-based coordination polymers, namely, [LnCu(3-tzba)2(H2O)4]n [Ln = Ho (1); Nd (2); Sm (3); Pr (4); 3-tzba = 3-(1H-tetrazol-5-yl)benzoate], were successfully synthesized through in situ [2 + 3] cycloaddition reaction under hydrothermal conditions. Compounds 14 are isomorphous 3D coordination frameworks with 1D anionic chains [Ln(3-tzba)2(H2O)4] linking the adjacent Cu(I) ions possessing an sql type net with Schläfli symbol (44). To our best knowledge, they are the first lanthanide-transition heterometal-organic coordination polymers obtained through in situ tetrazole synthesis. In addition, the thermal stability and magnetic property of 1 were also investigated.A series of novel three-dimensional (3D) Ln(III)–Cu(I) heterometallic tetrazole-based coordination frameworks, namely, [LnCu(3-tzba)2(H2O)4] [Ln = Ho (1); Nd (2); Sm (3); Pr (4); 3-tzba = 3-(1H-tetrazol-5-yl)benzoate], were successfully synthesized through in situ [2 + 3] cycloaddition reaction under hydrothermal conditions.Display Omitted► Heterometallic tetrazole-based coordination polymers have been synthesized. ► In situ synthesis of the 3-(1H-tetrazol-5-yl)benzoate. ► Magnetic studies indicated antiferromagnetic behavior for compound 1.
Keywords: Tetrazole; Heterometallic; In situ; Magnetism;

A multifunctional ligand of 4,8-disulfonyl-2,6-naphthalenedicarboxylic acid (H4-DSNDA) and its Eu(III) coordination polymer {(H-dpp)[Eu(DSNDA)(H2O)4](H2O)4}n (dpp = 1,3-di(4-pyridyl)propane) (1) have been synthesized. Compound 1 is a 2D anionic network based on the paddle-wheel Eu2(CO2)4 building blocks charge-balanced by the monoprotonated H-dpp molecules. Compound 1 shows intense red characteristic europium(III)-centered emission. The Eu(III) emissive state exhibits a single-exponential decay with a lifetime of 0.212 ms as measured at 613 nm after excitation at 346 nm. No observable emission peak arising from the DSNDA4− ligand (λem  = 408 nm) is observed in the emission spectrum of compound 1, indicating an efficient energy transfer occurs from DSNDA4− organic ligand to Eu(III) ions. The results reveal the large π-rich aromatic organic ligand is a suitable chromophoric moiety for sensitization of Eu(III) luminescence.This paper demonstrates an aromatic 4,8-disulfonyl-2,6-naphthalenedicarboxylate ligand sensitization of europium(III) luminescence in a two-dimensional coordination polymer.Display Omitted► Eu(III) coordination polymer; ► Paddle-wheel Eu2(CO2)4 building blocks; ► Europium(III)-centered emission; ► 4,8-Disulfonyl-2,6-naphthalenedicarboxylic acid.
Keywords: Eu(III) coordination polymer; 4,8-disulfonyl-2,6-naphthalenedicarboxylic acid; Luminescence;

Syntheses, structures and properties of chiral dinuclear zinc complexes with Schiff-base ligands by He-Rui Wen; Ying Wang; Jing-Lin Chen; Yun-Zhi Tang; Jin-Sheng Liao; Cai-Ming Liu (303-306).
Two couples of enantiomerically chiral dinuclear zinc complexes with Schiff-base ligands, [Zn2(R-L1)3](ClO4)·H2O (1) and [Zn2(S-L1)3](ClO4)·H2O (2), [Zn2(R-L2)3](ClO4) (3) and [Zn2(S-L2)3](ClO4) (4) (R-L1 or S-L1  =  R- or S-3-methoxy-6-(((methyl-2-pyridinylmethyl) imino)methyl)-Phenol, R-L2 or S-L2  =  R- or S-1-((1-(pyridin-2-yl)ethylimino)methyl) naphthalen-2-ol), were synthesized and characterized. The strong solid-state fluorescence emissions were observed at around 490 nm for 1 and 2 and 580 nm for 3 and 4 at room temperature, respectively, which are attributed to the intraligand charge-transfer excite state. The fluorescence emissions of 3 and 4 exhibit obvious red-shift relative to 1 and 2.Two couples of enantiomerically chiral dinuclear zinc complexes, [Zn2(R-L1)3](ClO4)·H2O (1) and [Zn2(S-L1)3](ClO4)·H2O (2), [Zn2(R-L2)3](ClO4) (3) and [Zn2(S-L2)3](ClO4) (4), have been synthesized and characterized. Complexes 14 show both chirality and photoluminescence properties. The strong solid-state emissions are observed at around 490 nm for 1 and 2 and 580 nm for 3 and 4, respectively, and the emissions of 3 and 4 exhibit obvious red shift relative to 1 and 2.Display Omitted► Two couples of chiral dinuclear zinc complexes were synthesized. ► Complexes 1-4 display both chirality and luminescence properties. ► The solid-state emissions are observed at around 490 nm for 1, 2, 580 nm for 3, 4. ► The emission bands of 3 and 4 exhibit obvious red shift relative to 1 and 2.
Keywords: Zinc complexes; Chiral Schiff-base; Crystal structure; Circular dichroism spectrum; Luminescence properties;

Observation of reversible three-step solid-to-solid phase transitions in a nickel-bis-1,2-dithiolene magnetic molecule solid by Shan-Shan Yu; Hai-Bao Duan; Wen-Bo Pei; Xuan-Rong Chen; Xiao-Ming Ren; Zheng-Fang Tian (307-311).
An ion-pair compound 1,6-bis(1-methylimidazolium)hexane bis(maleonitrio-dithiolato)nickelate was synthesized and structurally characterized. This compound crystallizes in the triclinic space group P-1, and the anions form the alternating stacks in the crystal. Reversible three-step solid-to-solid phase transitions occur at ~ 210, ~ 320 and ~ 432 K upon cooling. The entropy change of phase transition was estimated to be 25.4 J⋅K− 1⋅ mol− 1 and 9.97 J ⋅ K− 1⋅ mol− 1 for the transitions at ~ 320 and ~ 432 K, respectively. The hysteresis effect was observed in the χm–T plot for the transitions at ~ 210 and ~ 320 K. The mechanisms of transitions are discussed based on the crystal structure and thermal analyses.Three-step reversible solid-to-solid phase transitions, including two hysteretic magnetic and one crystal-to-plastic crystal transitions, occur in a 1-D S = 1/2 molecular magnetic solid.Display Omitted► Nickel-bis-1, 2-dithiolene anion combined with the ionic liquid component to yield a one-dimensional spin chain compound. ► Three-step reversible solid-to-solid phase transition. ► Hysteretic magnetic transition. ► Crystal-to-plastic crystal transition.
Keywords: Metal-bis-dithiolene complex; Hysteretic magnetic transition; Magnetoelastic interaction; Crystal-to-plastic crystal transformation;

A novel 3D layer-pillared metal-organic framework of [Cd3(IDC)(BDC)1.5(H2O)] n (1), (H3IDC = imidazole-4,5-dicarboxylic acid, H2BDC = 1,4-benzenedicarboxylic acid) was obtained by hydrothermal reaction, which contains rare planar hexnuclear Cd(II) cluster structural units and represents an unprecedented trinodal (4,5,14)-connected topology network. Furthermore, the thermal stability and luminescent property of 1 have also been examined.An unprecedented 3D (4,5,14)-connected layer-pillared metal-organic framework of [Cd3(IDC)(BDC)1.5(H2O)] n (1) (H3IDC = imidazole-4,5-dicarboxylic acid, H2BDC = 1,4-benzenedicarboxylic acid) containing rare hexnuclear Cd(II) clusters has been hydrothermally synthesized. Photoluminescent measurement illustrates 1 emits strong luminescence at 465 nm.Display Omitted► A novel 3D layer-pillared MOF based on mixed rigid ligands has been synthesized. ► It contains rare planar hexnuclear Cd(II) clusters as SBU. ► The framework displays a rare trinodal (4,5,14)-connected topology. ► Its thermal stability and luminescent property have also been investigated.
Keywords: Imidazole-4,5-dicarboxylic acid; 1,4-benzenedicarboxylic acid; Metal-organic frameworks (MOFs); Mixed-ligands; Luminescence;

Zinc(II) and cobalt(II) complexes with 3,5-di(pyridine-4-yl)benzoate: Structure and property by Chao Hou; Yue Zhao; Yi Lu; Peng Wang; Wei-Yin Sun (317-321).
Two new metal complexes with different 2D network topologies based on the 3,5-di(pyridine-4-yl)benzoic acid (HL), namely {[Zn(L)2]∙0.86H2O}n (1) and {[Co2(L)3(H2O)2]ClO4}n (2), have been prepared and characterized by single crystal and powder X-ray diffractions, IR, and thermogravimetric analyses. Complex 1 has a typical sql topology, whereas complex 2 is an unusual hxl one. Moreover, complex 1 shows luminescent property in the solid state at room temperature, and 2 exhibits overall weak antiferromagnetic coupling between the adjacent Co(II) ions.Two new complexes {[Zn(L)2]∙0.86H2O}n (1) and {[Co2(L)3(H2O)2]ClO4}n (2) [HL = 3,5-di(pyridine-4-yl)benzoic acid] with different network topologies were prepared and characterized.Display Omitted► Two-dimensional coordination frameworks with different structures and topologies. ► Different coordination modes of ligand. ► Fluorescence property and magnetic property.
Keywords: Zn(II) and Co(II) complexes; hxl net; Crystal structure; Fluorescence property; Antiferromagnetic interaction;

Preparation of the Co–Bi (1)/Co–Sb (2) binuclear oximate-bridged complexes, [BiIIICl3CoIII(ppko)3]·3.48CH3CN (1) and [SbIIICl2CoIII(ppko)3][ClO4]·0.78CH3OH (2), ppkoH = phenyl 2-pyridyl ketoxime, is presented. 1 is characterized as a new material, decomposing to cobalt metal particles, dispersed on a Bi-Co phase.Structure and properties of the Co-main group element (Bi, Sb) complexes are presented with the Co-Bi compound decomposing to the Bi-Co phase and Co metal particles.Display Omitted► Preparation of the Co-Bi /Co-Sb binuclear oxime-bridged complexes. ► A new Co-Bi material, decomposing to cobalt metal particles. ► EDX mapping used for analysis of the new materials.
Keywords: Bismuth(III); Antimony(III); Cobalt(III) Complexes; Phenyl 2-pyridyl ketoxime; Crystal structure; EDX;

Synthesis, structure and catalytic activity of dicarbene dipalladium complexes with different alkane bridge by Jianfeng Zhao; Long Yang; Kaiqi Ge; Qian Chen; Yongzhong Zhuang; Changsheng Cao; Yanhui Shi (326-329).
A series of di-NHC dipalladium complexes Pd2LPy2Cl4 (L = LC3, LC5, LC6 and LC10) with alkyl bridges of different chain lengths were prepared. The molecular structures of Pd2LC3Py2Cl4 (1) and Pd2LC6Py2Cl4 (3) were determined by X-ray diffraction studies. The influence of the different bridges on the structure and reactivity of the complexes was studied. The structure of complex 3 consists of two pseudo-square-planar subunits in a trans configuration, however complex 1 shows an X configuration due to π–π stacking of both imidazole rings and pyridine rings. The catalytic activity of the new binuclear palladium complexes was successfully tested in the Mizoroki–Heck reaction of styrene with aryl bromides. The length of the bridged ligands had some effect on the yield and regioselectivity of the products.A series of bis-NHC di-palladium complexes with alkyl bridges of different chain lengths have been prepared. The X-ray structure of two complexes was studied. π–π stacking plays an important role in the configuration of the palladium subunits in the solid structures. The complexes showed good catalytic activity for the arylation of olefins.Display Omitted► Novel di-NHC di-Pd complexes bridged with alkane have been synthesized. ► The molecular structures have been determined. ► The two palladium subunits are in different configuration. ► π–π stacking plays an important role in the configuration of the palladium subunits. ► The complexes showed good catalytic activity for the arylation of olefins.
Keywords: Dipalladium; N-heterocyclic carbene; Alkane bridge, X-ray structure; Heck reaction;

The effect of several triazole compounds (1,2,4-triazole and its 3-ethoxycarbonyl derivative as well as 1,2,3-triazole, its 4-[N-methyl(2,2,2-trifluoroacetamide)] derivative and two 1,2,3-triazole ribonucleosides) and their complexes with transition metal ions (Co2 +, Ni2 +, Zn2 + Cd2 + and Cu2 +) on the catalytic activity of antigenomic HDV ribozyme was tested at different pH values. Investigated at pH 7.5, 1,2,3- and 1,2,4-triazole derivatives only slightly inhibited Mg2 +-induced catalytic cleavage of the ribozyme. In comparison, Co2 + and Ni2 + complexes of 1,2,3-triazole and their derivatives, namely, N-(1,2,3-triazol-4-yl)methyl-2,2,2-trifluoroacetamide and 1-β-d-ribofuranosyl-1H-1,2,3-triazole-4-carboxylic acid amide inhibited the cleavage reaction 4–5-fold more strongly.Additionally, the application of Zn2 + complexes of 1,2,3- and 1,2,4-triazole instead of catalytic Mg2 + ion, promoted the cleavage activity of the ribozyme at pH 5.5. The 1,2,3-triazole-Zn2 + complex was found to be the most effective.We report that complexes of triazole derivatives with transition metal ions (Co2 +, Ni2 +, Zn2 +, Cd2 +, and Cu2 +) modulate the catalytic activity of antigenomic HDV ribozyme in a pH-dependent manner.Display Omitted► Interaction complexes of triazole-transition metals with HDV ribozyme were tested. ► Impact of complexes on the catalytic activity of ribozyme is strongly pH dependent. ► At physiological pH complexes inhibit the catalytic activity of HDV ribozyme. ► Complexes of 1,2,4-triazole derivatives with Co2 + and Ni2 + are the most active. ► At lower pH 1,2,3-triazole-Zn2 + complex promotes cleavage of HDV ribozyme.
Keywords: Triazole derivatives–metal ion complexes; HDV ribozyme; pH dependence;

A novel N,N,O-tridentate ligand of 8-hydroxyquinoline (Q) derivative, namely 2-(benzimidazol-2-yl)-8-butoxyquinolin(BIBQ), has been synthesized with 8-hydroxyquinadine and o-diaminobenzene as the starting materials. The as-prepared ligand reacted with diethylzinc to give Zn(II) complex. The ligand and complex were then characterized by carbon nuclear magnetic resonance (13C NMR), proton nuclear magnetic resonance (1H NMR), mass spectra (MS) and elemental analysis (EA). In addition, the thermal performance, the electrochemical performance and the photoluminescence performance of zinc complex were investigated. The results showed that the decomposition temperature (onset) of the complex is 290 °C, indicating relatively higher thermal stability. Moreover, the energy levels of the highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO) and the energy gap were calculated to be − 5.41, − 2.74 and 2.67 eV, respectively. The emission spectra of the complex in solution and solid were also studied and obviously emitted fluorescence at λmax  = 493 nm.A novel N,N,O-tridentate ligand of 8-hydroxyquinoline derivative and its zinc complex have been synthesized and their structures were characterized by carbon nuclear magnetic resonance (13C NMR), proton nuclear magnetic resonance (1H NMR), mass spectra (MS) and elemental analysis (EA).In addition, we have investigated the performances of zinc complex.Display Omitted► The presence of butoxy group can decrease the symmetry of the ligand. ► The presence of butoxy group in a ligand can increase the lipophilicity of a complex. ► This Zn(II) complex exhibits relatively high thermal stability.
Keywords: 8-Hydroxyquinoline derivatives; Zinc complex; Thermal stability; Electrochemical performance;

Two new manganese(II) coordination polymers, [Mn2(bpe)2(4-Brip)2]n (1) and {[Mn3(H2O)2(H-bpp)2(5-Brip)4]·H2O}n (2), were prepared through hydrothermal reactions of Mn(II) acetate with H2-4-Brip or H2-5-Brip (H2-4/5-Brip = 4/5-bromoisopthaliac acid) and the bipyridyl-type co-ligands bpe or bpp (bpe = 1,2-bi(4-pyridyl)ethane and bpp = 1,3-bi(4-pyridyl)propane). The two complexes were characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis and X-ray single-crystal diffraction. Complex 1 has a complicated (3,5)-connected 3D 3-fold interpenetrating network with a Schläfli symbol of (42.65.83)(42.6), constructed of the ribbon-like chains having dimeric [Mn(COO)]2 units bridged by 4-Brip. Complex 2 contains isophthalato-bridged trimanganese clusters as building units, which are linked by 5-Brip anions to form a 1D ladder-like chain with unidentate coordinated H-bpp decorated as pendants. And the chains are further linked by N―H∙∙∙O and O―H∙∙∙O hydrogen bonding to generate a 2D interlocked architecture. Dominant antiferromagnetic couplings were observed in complexes 1 and 2.Two new manganese(II) coordination polymers were synthesized and characterized. Complex 1 exhibits a complicated 3D 3-fold interpenetrating network. Complex 2 possesses a 2D layer structure, and exists extensive hydrogen-bonding interactions.Display Omitted► Two Mn(II) complexes were synthesized and characterized. ► Dominant antiferromagnetic couplings in 1 and 2 ► Compared with other isophthalate derivative complexes, the substituted groups have an effect on final structures.
Keywords: Bromoisophthalate; Manganese(II) complex; Magnetic properties;