Inorganic Chemistry Communications (v.60, #C)

Contents List (iii-xi).

Structural characterization of ferromagnetic bridged-acetato and -dichlorido copper(II) complexes based on bicompartmental 4-t-butylphenol by Salah S. Massoud; Thomas Junk; Radovan Herchel; Zdeněk Trávníček; Masahiro Mikuriya; Roland C. Fischer; Franz A. Mautner (1-3).
The reaction of Cu(II) salts with 2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-t-butylphenol (Lt-Bu-OH) afforded two bridged-phenoxido/hydroxido complexes. The dinuclear bridged acetate species [Cu2(μ-Lt-Bu-O)(μ-CH3COO)](PF6)2 (1) and the 1D polymeric doubly-bridged-chlorido {[Cu2(μ-Lt-Bu-OH)(μ-Cl)2](ClO4)2·4H2O}n (2). The two complexes were structurally characterized. Both complexes revealed ferromagnetic interactions; moderate in complex 1 (J  = + 30.8 cm− 1) and very weak (J  = + 2.25 cm−1) in 2.Two bridged Cu(II) complexes [Cu2(μ-Lt-Bu-O)(μ-CH3COO)](PF6)2 (1) and {[Cu2(μ-Lt-Bu-OH)(μ-Cl)2](ClO4)2·4H2O}n (2) based on the phenolic binucleating ligand, Lt-Bu-OH were synthesized, structurally and magnetically characterized.Display Omitted
Keywords: Copper; Polynuclear complexes; Bridged phenolate; Bridged chloro; Crystal structure; Magnetic properties;

Ionothermal synthesis, fluorescence, and DFT calculation of three lanthanide-based metal-organic frameworks by Wen-xian Chen; Jia-qi Bai; Zao-hong Yu; Qiu-ping Liu; Gan-ning Zeng; Gui-lin Zhuang (4-7).
Three lanthanide-based metal-organic frameworks (MOFs), [Ln(SIP)(HSIP)][EMIm]2, (Ln = La(1), Nd(2) Eu(3); H2SIP = 5-sulfoisophthalic acid; EMImBr = 1-ethyl-3-methyl-imidazole bromine), were obtained under the ionic liquid medium. Crystal structure analysis reveals that there are two-dimensional metal-organic frameworks, which are built from the connection of {Lnn} chains by SIP3 − ligands. It is found that EMIm+ cations are filled in the void between 2D layers. Interestingly, the whole framework shows one new topology with the symbol of [3 · 42]2[34  · 46  · 56  · 68  · 73  · 8]. Luminescence measurement exhibits that compound 3 has good emission property. Furthermore, DFT calculation results confirm that the emission mechanism can be attributed to the transition of ff transition of Eu(III) ions, where SIP3 − ligand acts as the role of electron carrier.Three ionothermally obtained lanthanide-based MOFs exhibit new two-dimensional frameworks and reveal the emission mechanism by a combination of experiment and DFT calculation.Display Omitted
Keywords: Metal-organic framework; Ionothermal; Luminescence; DFT calculation;

A new porphyrin–polyoxometalate hybrid nanoparticle was synthesized by the ionic assembly between trans-diaquo[5,10,15,20-tetrakis(4-pyridinium)porphyrinato]tin(IV) cation (SnP) and phosphomolybdate anion (POMo) in aqueous solution. UV–vis spectroscopic investigation on SnP–POMo nanoparticles supports that J-aggregation mainly occurs in SnP–POMo rather than H-aggregation. The influences of temperature or pH to the formation of SnP–POMo nanoparticle were examined. DLS measurements revealed that the average hydrodynamic diameter of SnP–POMo in water is ca. 245 nm with narrow distributions in size. The photocatalytic hydrogen production from water by the SnP–POMo sensitization exhibited higher activity than that of SnP under visible light irradiation.Porphyrin–polyoxometalate hybrid nanoparticles (SnPPOMo) were prepared with tin(IV)-porphyrin cations and polyoxomolybdate anions. The average hydrodynamic radius amounts to ca. 245 nm with narrow distribution in size. SnPOMo exhibits a broad absorption in the range of 400–900 nm, and photocatalytic hydrogen production was performed by its visible light sensitization.Display Omitted
Keywords: Ionic assembly; Porphyrin; Polyoxometalate; Hybrid nanoparticles; Photocatalysis;

A novel dioxidovanadium-based nickel complex [Ni2(C2O4)(dpa)4][(C4H6O4)(VO2)]2·2[CH3OH] (dpa = 2,2′-dipyridine amine) was in situ synthesized by a facile procedure and further used as catalyst to oxidize sulfur-containing heterocyclic compounds to corresponding sulfones using molecular oxygen as the oxidant and isobutyl aldehyde as the sacrificial agent in model oil under mild conditions.A novel dioxidovanadium-based nickel complex [Ni2(C2O4)(dpa)4][(C4H6O4)(VO2)]2·2[CH3OH] (dpa = 2,2′-dipyridine amine) was in situ synthesized by a facile procedure and further shows high catalytic activity to oxidize sulfur-containing heterocyclic compounds to corresponding sulfones using molecular oxygen as the oxidant and isobutyl aldehyde as the sacrificial agent in model oil under mild conditions.Display Omitted
Keywords: In situ synthesis; Dioxidovanadium-based complex; Oxidative desulfurization; Catalytic reaction;

Complexes of general formula [Eu(fod)3·L], [Tb(fod)3·L] and [Gd(fod)3·L] (where fod = 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octadionate; L = 4,4-diphenyl-2,2-dipyridyl or/and chloride of 1,10-phenantrolinium) were synthesized by reacting the corresponding salt of terbium and gadolinium with β-diketone(fod) and other ligands, and the precursor Eu(fod)3·2H2O with diphenylbipy and phenCl ligands. The thermal decomposition of these complexes along with description of some emitting materials is discussed in details. We focused on those complexes emitting in the visible region, which can be used in lighting industry (e.g., for the preparation of photo- and electro-luminescent devices) and for biological immunoassays. The thermal decompositions of Eu(fod)3·L, Tb(fod)3·L and Gd(fod)3·L are best described by R2 and R3 kinetic models. Some selected results of our work concerning the synthesis of highly luminescent complexes for application in lighting and light conversion technologies are reported. Such materials have been obtained by combining the peculiar luminescence properties of Eu3 + and Tb3 + antenna complexes with β-diketone (fod).Molecular structure of the complex (A) Eu(fod)3·fenCl and (B) Tb(fod)3·fenCl calculated by model sparkle.Display Omitted
Keywords: Luminescence; Lanthanide complexes; Kinetic; Thermal decomposition;

A 3D-diamond-like metal–organic framework: Crystal structure, nonlinear optical effect and high thermal stability by Lihua Wang; Yingxiang Ye; Liuqin Zhang; Qianhuo Chen; Xiuling Ma; Zhangjing Zhang; Shengchang Xiang (19-22).
A new metal–organic framework [Zn(cpt)(ATZ)]n (1, HATZ = 5-amino-1H-tetrazol, Hcpt = 4-(4H-1,2,4-Triazol-4-yl)benzoic acid), has been solvothermally synthesized and structurally characterized by single crystal X-ray diffraction. Structural analysis shows that compound 1 is a three-dimensional (3D) framework with 3-fold interpenetrated diamond topology where the Zn(II) centers are all 4-coordinated. Compound 1 exhibits high thermal stability up to 370 °C, and weak second-order nonlinear optical coefficient as ca. 0.13 times as that of potassium dihydrogen phosphate (KDP), and also displays blue photoluminescence at room temperature.A new mixture ligand three-dimensional framework Zn(II)-MOFs with a 3-fold interpenetrated diamond net has been synthesized and characterized, which exhibits weak second-order nonlinear optical coefficient comparable to KDP, and displays blue photoluminescence and high thermal stability.Display Omitted
Keywords: Metal–organic frameworks; Second-order nonlinear optical; Interpenetrated diamond topology; Thermal stability;

The ligand-bridged dimers [Re(CO)3(μ-H2salet)]2 (1) and [{Re(CO)3}2(μ-salpd)] (2) are formed by the reactions of [Re(CO)5Cl] with the potentially heptadentate Schiff base 2,2′,2″-tris(salicylideneimino)triethylamine (H3salet) and the hexadentate N 1-(3-(2-hydroxybenzylidene-amino)propylamino)ethyl)-benzylidenepropane-1,3-diamine (H2salpd) respectively. In 1, the two H2salet ligands bridge two fac-[Re(CO)3]+ moieties. Mono-dentate coordination is by a neutral phenone oxygen atom, generated by the conversion of one salicylideneimine entity to an iminium zwitter-ion. In 2 each fac-[Re(CO)3]+ core resides in a ‘3 + 0’ environment. In both complexes π–π interaction between the phenolate rings contribute to the stability. The crystal structures of 1 and 2 were determined by X-ray single crystal diffraction. Spectroscopic results are also reported.The ligand-bridged dimers (μ-H2salet)2[Re(CO)3]2 (1) and (μ-salpd)[Re(CO)3]2 (2) are formed by the reactions of [Re(CO)5Cl] with the potentially heptadentate Schiff base 2,2′,2″-tris(salicylideneimino)triethylamine (H3salet) and the hexadentate N 1-(3-(2-hydroxybenzylidene-amino)propylamino)ethyl)-benzylidenepropane-1,3-diamine (H2salpd) respectively. In 1, the two H2salet ligands bridge two fac-[Re(CO)3]+ moieties in a ‘2 + 1’-type donor atom set. Mono-dentate coordination is by a neutral phenone oxygen atom, generated by the conversion of one salicylideneimine entity to an iminium zwitter-ion. In 2 each fac-[Re(CO)3]+ core resides in a ‘3 + 0’ environment. In both complexes π–π interaction between the phenolate rings contribute to the stability.Display Omitted
Keywords: Rhenium(I); Multidentate Schiff bases; Ligand-bridged dimers; X-ray crystal structures;

Four novel heterometallic tetranuclear 3d–4f complexes M2Dy2L10(phen)2 (M = Co (1), Ni (2), Cu (3) and Zn (4); HL = 4-trifluoromethylbenzoic acid, phen = phenanthroline) have been synthesized hydrothermally and characterized by single crystal X-ray diffraction study, IR, elemental analysis and thermal gravimetric analyses. The structures of 1 and 4 are isostructural and the completely deprotonated L ligands adopt μ 2: η 1, η 1 coordination mode to bridge adjacent metal ions which further connect into 1D chains by hydrogen bonds. The tetranuclears in complex 2 were linked by L ligands with μ 2: η 1, η 2 and μ 2: η 1, η 1 coordinated patterns and spread into 2D layers through hydrogen bonds. In complex 3 L ligands possess the same coordinated styles with 2 and a 3D supramolecular network was fabricated via hydrogen-bonding interactions. Dynamic magnetic susceptibility studies reveal slow magnetic relaxation processes for 1 and 3, suggesting SMM type behavior for these compounds.Four tetranuclear 3d–4f complexes based on 4-trifluoromethylbenzoic acid and 1,10-phenanthroline (phen) have been synthesized and characterized. They adopt distinct coordination modes and various supramolecular frameworks. Complexes 1 and 3 exhibit slow magnetic relaxation processes, suggesting SMM type behavior.Display Omitted
Keywords: Crystal structures; 3d–4f complexes; Hydrothermal synthesis; Magnetic properties;

Two inorganic–organic hybrid compounds based on Strandberg-type phosphomolybdates (abbreviated as {P2Mo5O23}6 −) complexes [H3O]2[Cu2(Pyim)2(H2O)3][P2Mo5O23] · 6H2O (1) and [Cu3(Pyim)3(H2O)4][P2Mo5O23] · 7H2O (2) were successfully synthesized at different pH values under hydrothermal conditions. Both 1 and 2 are based on the {P2Mo5O23}6 − clusters connected by copper complexes to generate one dimensional chain. The magnetic analyses of compounds 1 and 2 indicate antiferromagnetic interactions between copper ions.Two inorganic–organic hybrid compounds [H3O]2[Cu2(Pyim)2(H2O)3][P2Mo5O23] · 6H2O (1) and [Cu3(Pyim)3(H2O)4][P2Mo5O23] · 7H2O (2) are based on the {P2Mo5O23}6 - clusters connected by copper complexes to generate one dimensional chains. The magnetic analyses of compounds 1 and 2 indicate antiferromagnetic interactions between copper ions.Display Omitted
Keywords: Polyoxometalate; Crystal structure; Magnetic property; Electrochemistry;

Product of dissolution of V2O5 in the choline chloride–urea deep eutectic solvent by Peter Billik; Peter Antal; Róbert Gyepes (37-40).
The previously reported high solubility data for V2O5 in the deep eutectic solvent of choline chloride and urea (ChCl–urea) is the result of forming [H2V10O28]4 − complex anion.Storing this as-prepared solution for about three months at 20 °C, a new compound, [(CH3)3N(CH2)2OH]4[H2V10O28]·2(NH2)2CO (1), was obtained. The solid-state structure is assembled of dihydrogendecavanadate(V) anions, choline cations and molecules of urea. The crystal structure is further stabilized by electrostatic interactions and by O–H⋯O and N–H⋯O hydrogen bonds. The 51V NMR spectroscopy detected the decavanadate anion in the as-prepared solution.Display Omitted
Keywords: Deep eutectic solvent; Vanadium pentoxide; Decavanadate;

Here, high purity octa(3-mercaptopropyl) POSS has been synthesized and subsequently reacted with a variety of alkenes via radical and base catalyzed thiol-ene addition reactions. Among them a unique antibacterial agent, eugenyl methacrylate (EgMA), was attached yielding an organic soluble octaEgMA-POSS compound as a potential antibacterial additive for polymeric systems.

The complexes [ReI (L–L)(CO)3Cl] with L–L = lumazine and folic acid were prepared and their electronic spectra were measured. The free ligands L–L, as well as both complexes, show an emission which is attributed to the fluorescence of L–L. This luminescence is apparently facilitated by excited state proton transfer.Light absorption by Re(L–L)(CO)3Cl with L–L = lumazine and folic acid leads to an ILCT with a subsequent IL-fluorescence.Display Omitted
Keywords: Luminescence; Fluorescence; Rhenium(I); Lumazine; Folic acid;

The new transition metal coordination polymer, namely [Ag(Hcpna)]n (1) (H2cpna=5-(4-carboxyphenyl) nicotinic acid) has been synthesized under hydrothermal conditions and characterized. Interestingly, when this compound was immersed in the different metal ion solutions, it shows highly selective sensing for Cd2 + based on significant luminescence enhancement. What's more, the compound 1 can serve as an antenna for sensitizing the visible-emitting of the lanthanide cations to exhibit their characteristic emissions in solution.A novel bimodal 2D silver coordination polymer has been successfully synthesized and characterized. Complex 1 provides an ideal luminescence sensor for selective probing Cd2 + ions. What's more, the complex 1 can serve as an antenna for sensitizing the visible-emitting of the lanthanide ions to exhibit their characteristic emissions.Display Omitted
Keywords: Coordination polymer; Luminescence properties; Sensor; Sensitization;

Dual-nodal PMMA-supported Eu3 +-containing metallopolymer with high color-purity red luminescence by Xinyu Zhang; Zhao Zhang; Lin Liu; Chao Yu; Xingqiang Lü; Xunjin Zhu; Wai-Kwok Wong; Richard A. Jones (51-53).
Based on chemical grafting of the complex monomer [Eu(TTA)3(4-vinyl-Py)2] (HTTA = 2-thenoyltrifluoroacetylacetate, 4-vinyl-Py = 4-vinyl-pyridine) with two active vinyl groups and MMA (methyl methacrylate), the dual-nodal PMMA-supported metallopolymers with high color-purity Eu3 +-based luminescence are obtained. The physical properties show that their luminescent properties (τ obs  = 494–552 μs and Ф Eu L  = 50–55%) are distinctively enhanced from copolymerization in comparison with those (τ obs  = 470 μs and Ф Eu L  = 44%) of the complex monomer besides the improvement of thermal-stabilities.In the obtained dual-nodal PMMA-supported metallopolymers Poly{[Eu(TTA)3(4-vinyl-Py)2]-co-MMA}, high color-purity Eu3 +-based luminescence (τ obs  = 494–552 μs and Ф Eu L  = 50–55%) is observed besides good thermal-stabilities.Display Omitted
Keywords: Dual-nodal PMMA-supported metallopolymer; Tris-β-diketonate Eu3 +-complex; High color-purity Eu3 +-based luminescence;

A series of triphenylamine substituted dipyrrinato metal complexes (18) have been synthesized. The mononuclear type complexes 16 have Ni(II), Co(II), Pd(II), In(III), and Zn(II) metal ions in the core. The binuclear type complexes 7 and 8 have Zn(II) metal ion in the center. All the compounds (18) were characterized by HRMS, NMR, IR, UV–vis absorption, cyclic voltammetry and fluorescence techniques. The presence of large electron rich triphenylamine moiety at dipyrrin ligands affected the spectral properties of complexes. Except Co(II) complex, other metal complexes exhibited blue shifted absorption maxima in UV–vis studies. The In(III) and Zn(II) metal complexes 46 showed red shifted emission maxima in fluorescence compared to their corresponding phenyl analogues. Complexes 38 exhibited good Stokes shifts in the range of 4600 to 7000 cm− 1 with reduced quantum yields. Singlet state lifetimes of complexes 38 were in the range of 2 to 4 ns; also the decrease in radiative decay constants k r and the increase in non-radiative decay constants k nr were in line with the quantum yield data. CV studies of complexes 18 showed anodic shifts in the oxidation potentials, suggesting that meso-triphenylamine group has affected the electronic properties of complexes by making them difficult to oxidize.A series of triphenylamine substituted dipyrrinato metal complexes having Zn(II), In(III), Pd(II), Ni(II) and Co(II) metal ions have been reported. Detailed synthesis, photophysical and electrochemical studies have been described. The spectral properties were affected by the electron donating triphenylamine moieties. Electrochemical studies revealed anodic shifts for all complexes.Display Omitted
Keywords: Dipyrrins; Triphenylamine dipyrrinato complex; Dinuclear metal complex;

Reaction of silver(I) with robust halido complexes of Ir(III) leads to second sphere coordination rather than halide abstraction. Two hexa-coordinated pseudo-octahedral silver(I) complexes [(CH3CN)3IrX3AgX3Ir(NCCH3)3]+ (X = Cl, Br) have been synthesized and structurally characterized as PF6 and SbF6 salts, respectively. The synthesis and crystal structure of the new, mononuclear complex, [IrBr3(NCCH3)3], are also reported along with spectroscopic characterization of [IrX3(NCCH3)3] and the trinuclear silver complexes. The electronic structures are analyzed in the framework of ligand field theory and by comparison with high-level correlated multireference ab initio calculations. The ligand field strength of the heavier halide complexes is found to be significantly less sensitive to outer-sphere complexation as compared to the pronounced outer sphere ligation effects commonly observed for fluoride complexes.Silver(I) is complexed by tri-halide complexes of kinetically robust iridium(III).Display Omitted
Keywords: Outer sphere coordination; Silver(I); Iridium; Ligand field theory;

By the rational self-assembly of trivacant Keggin precursor [B-α-SbW9O33]9 − with Fe3 + and Ce3 + cations in the conventional aqueous solution, a novel FeIII–CeIII heterometallic sandwich-type tungstoantimonate [Ce(H2O)8][Ce(H2O)6] [Fe4(H2O)10(B-β-SbW9O33)2]·16H2O (1) has been successfully synthesized and further structurally characterized by elemental analyses, IR spectra and single-crystal X-ray diffraction. Structural analysis indicates that the 2-D infinite sheet of 1 consists of the Krebs' sandwich-type [Fe4(H2O)10(B-β-SbW9O33)2]6 − subunits and Ce3 + linkers. 1 represents the rare purely inorganic FeIII–CeIII heterometallic tungstoantimonate derivative with the 2-D infinite sheet. The electrochemical and electrocatalytic properties of 1 have been systemically studied in 0.5 mol·L− 1 Na2SO4  + H2SO4 supporting electrolyte, moreover, 1 exhibits the obvious electrocatalytic activity towards the reduction of BrO3 and NO2 .A FeIII–CeIII heterometallic sandwich-type tungstoantimonate with novel 2-D extended structure has been synthesized and its electrochemical properties have been investigated.Display Omitted
Keywords: Self-assembly; Tungstoantimonate; 2-D infinite sheet; Electrochemistry;

A class of 3s–5d–4f mixed metal substituted sandwich-type arsenotungstates [H2N(CH3)2]8H3[LnNa(H2O)4(OH)WO(H2O) (B-α-AsW9 O33)2]·8H2O [Ln = LaIII (1), CeIII (2), PrIII (3)] have been isolated from an aqueous solution reaction system (pH = 4) of Na2WO4·2H2O, C2H7N·HCl, NaAsO2 and Ln(NO3)3·6H2O and structurally characterized by elemental analyses, IR spectra, UV spectra and single-crystal X-ray diffraction. It is the most prominent in 13 that the [LnNa(H2O)4(OH) WO(H2O)(B-α-AsW9O33)2]11 − polyanion consists of two trivacant Keggin [B-α-AsW9O33]9 − moieties linked by one [WO(H2O)]4 + group and a dimeric [LnNa(H2O)4(OH)]3 + group resulting in the special 3s–5d–4f mixed metal substituted sandwich-type assembly. Interestingly, lanthanide and sodium ions simultaneously occupy the two positions located at the central belt of 13 with the site occupancy of 50% for each position. Moreover, the electrochemical and electrocatalytic properties of only 1 and 2 have been measured by cyclic voltammetry (CV) in 0.5 mol·L− 1 Na2SO4  + H2SO4 aqueous solution. 1 and 2 illustrate electrocatalytic activities for the hydrogen peroxide reduction.A class of 3s–5d–4f mixed metal substituted sandwich-type arsenotungstates [H2N(CH3)2]8H3[LnNa(H2O)4(OH) WO(H2O)(B-α-AsW9O33)2]·8H2O [Ln = La3 + (1), Ce3 + (2), Pr3 + (3)] have been synthesized and characterized.Display Omitted
Keywords: Polyoxometalate; Arsenotungstate; Electrochemistry;

Continuing our work on the synthesis of MoO2L2 and MoO3LALB that show excellent anti-cancer activities in vitro, the MoL3 have been synthesized by the solvothermal reaction of Na2MoO4 with catechols and 1,2-DPA in the mixed solvent of MeCN/MeOH. X-ray diffraction revealed that Mo in chiral octahedral geometry coordinate with three catechol ligands formed three five-membered rings, and the [Mo(C6H4O2)3] are linked by hydrogen bonds Mo(OC6H4)O…H–N(C4H8O)N–H…O(C6H4O)Mo through the by-product (C4H8N2O) that are formed by one 1,2-DPA with one CO2 on the catalysis of Mo-complex. Also, we have disassembled bulk crystal into nano-aggregates, and under TEM mono-lamella morphology of nanostructures was observed, which agrees well with the previous conclusion that the morphologies of the nano-aggregates are associated with the quantum motifs in their crystal lattices. [Mo(C6H4O2)3] have also been characterized by UV–vis spectra, cyclic voltammogram and thermogravimetric analysis.Synthesis of [Mo(C6H4O2)3] and its nanostructure and C4H8N2O formed by 1,2-propanediamine and CO2 on the catalysis of Mo-complex.Display Omitted
Keywords: Mo(cat)3; Multi-layer; Mono-nano-lamella; Catalysis;

An interpenetrated framework based on pentanuclear tetrahedral cluster with four-connected mdf network by Jia-Jia Deng; Bai-Qiao Song; Jun Liang; Yan-Qing Jiao; Xue-Song Wu; Liang Zhao; Kui-Zhan Shao; Zhong-Min Su (82-86).
A new three-dimensional metal–organic framework constructed form pentanuclear tetrahedral cluster and linear dicarboxylic acid ligand, [Zn5(btz)6(ndc)2(H2O)]·3DMA (1) (btz = benzotriazole, H2ndc = 1,4-naphthalenedicarboxylic acid) has been synthesized by the modular building blocks (MBBs) strategy under the solvothermal condition. Single X-ray diffraction reveals that 1 is a two-fold interpenetrated framework with mdf topology, in which pentanuclear {Zn5(btz)6} cluster acts as a 4-connected node. Moreover, the luminescent properties of 1 dispersed in different metal ions and solvents have been investigated systematically.A novel three-dimensional (3D) twofold interpenetrated MOF is based on pentanuclear tetrahedral cluster unit. Its structure contains four-connected uninodal net: mdf net. The mdf net is an 86 net with the long vertex symbol (81.83.84.84.84.84).Display Omitted
Keywords: Metal–organic frameworks; Pentanuclear tetrahedral cluster; Topology; Photoluminescent;

Water soluble choline-labeled CdSe/ZnSe/ZnS quantum dot (QD) bioconjugates were synthesized by attaching a thiolated choline analogue to the core-shell QD surface. Characterization was conducted by absorption and luminescence spectroscopy and scanning electron microscopy. QDs with diameters of 5–6 nm resulted and exhibited a luminescence maximum at 663 nm in aqueous solution.Water soluble choline- labeled CdSe/ZnSe/ZnS core-shell quantum dots were synthesized and exhibit strong luminescence in aqueous solution.Display Omitted
Keywords: CdSe/ZnSe/ZnS quantum dots; Neurotransmission; Choline; Alzheimer's disease; Choline uptake;

Two cobalt complexes containing different nitronyl nitroxide radicals: Structure and magnetic properties by Yu-Kun Kong; Xue-Hui Lv; Xiang-Lan Wang; Chen-Xi Zhang; Qing-Lun Wang (91-94).
Two Co(II) complexes based on different nitronyl nitroxide radicals were synthesized and characterized structurally and magnetically: [Co(hfac)2(NITPhp-Cl)(phenol)](1) and [(Co(hfac)2(NITPh-(OCH3)3)2)(Co(hfac)2(H2O)2)] (2) [hfac = hexafluoroacetylacetonate, NITPh-p-Cl = 2-(4′-chlorophenyl)-4,4,5,5-tetramethylimida-zoline-1-oxyl-3-oxide, NITPh(OCH3)3  = 2-(3′,4′,5′-trimethoxyphenyl) -4,4,5,5-tetramethylimida-zoline-1-oxyl-3-oxide]. X-ray crystal structure analysis revealed that the Co(II) ions in complexes 1 and 2 are six-coordinated with slightly distorted octahedral geometry. The packing diagram of complex 2 shows a 3D supermolecular structure formed by intermolecular hydrogen bond interactions. Variable temperature magnetic susceptibility measurement studies revealed that complexes 1 and 2 exhibit antiferromagnetic interactions between Co(II) and radicals with J  = − 0.1 cm− 1 (1) and J  = − 3.43 cm− 1 (2), respectively.Two Co(II) complexes based on different nitronyl nitroxide radicals were synthesized and characterized structurally and magnetically: [Co(hfac)2(NITPhp-Cl)(phenol)](1) and [(Co(hfac)2(NITPh-(OCH3)3)2)(Co(hfac)2(H2O)2)] (2). X-ray crystal structure analysis revealed that the Co(II) ions in complexes 1 and 2 are six-coordinated with slightly distorted octahedral geometry. The packing diagram of complex 2 shows a 3D supermolecular structure formed by intermolecular hydrogen bond interactions. Variable temperature magnetic susceptibility measurement studies revealed that complexes 1 and 2 exhibit antiferromagnetic interactions between Co(II) and radicals with J  = − 0.1 cm− 1 (1) and J  = − 3.43 cm− 1 (2), respectively.Display Omitted
Keywords: Nitronyl nitroxide; Crystal structures; Transition metal; Magnetic properties;

By employing 5-oxyacetate-isophthalic acid (H3OABDC) and cadmium nitrate, a new unusual three-dimensional (3D) metal–organic framework (MOFs), namely, {[Cd3(OABDC)2(H2O)5]·2H2O} n (1) was solvothermally synthesized and structurally characterization by single-crystal X-ray diffraction, elemental analysis and thermal analysis. Furthermore, solid-state luminescent property has been investigated.One new three-dimensional compound {[Cd3(OABDC)2(H2O)5]·2H2O} n based on 5-oxyacetateisophthailic acid (H3OABDC) has been synthesized. The compound has a (4,5)-connected fsx-4,5-R-3m net with point symbol {43·63}{43·66·8}.Display Omitted
Keywords: Coordination polymer; Crystal structure; Hydrogen bonds; Cd(II) compound;

Within the scope of a systematic study of eight-coordinate ZrIV chelates, a mixed potassium trioxalatozirconate (IV) complex, namely K2[Zr(C2O4)2(μ-C2O4)] · 2H2O, has been synthesized. Its structure framework represents a zirconium (IV) carboxylate polymer displaying interesting polymeric zigzag chains of ZrO8 units running parallel to the c axis. Stereo-chemical study of polyhedral eight-vertex structure revealed that in ZrO8 the average in the coordination polyhedral is a Biaugmented trigonal prism J50 chelate. Hirshfeld surface and fingerprint plot analysis revealed that O · · · O intermolecular interactions are the most important ones accountable for the reinforcement of the supramolecular assembly of the coordination polymers. The thermal decomposition has been studied by coupled ATD-TGA and supplemented by infrared and Raman emission spectroscopy as a function of temperature which nicely corroborated the crystal structure and suggest a deformation in the Zr–O chelate with departure of water molecules.The structure of K2[Zr(C2O4)2(μ-C2O4)] · 2H2O displays interesting polymeric zigzag chains of ZrO8 units. Stereo-chemical study of polyhedral eight-vertex structure revealed that in ZrO8 the average in the coordination polyhedral is a Biaugmented trigonal prism J50 chelate with a strong deformation. Hirshfeld surface analysis exposes interactions experienced by oxalate ligands.Display Omitted
Keywords: Zirconium–potassium oxalate complex; Stereo-chemical study; Hirshfeld surface analysis; Thermal decomposition;

Two lanthanide(III) complexes containing tetraselenidoantimonate ligand [Sm(peha)(μ-1κ2:2κ-SbSe4)]n (1), and [Eu(peha)(1κ2-SbSe4)] (2) (peha = pentaethylenehexamine) were solvothermally prepared by reactions Sb, Se and LnCl3 in pentaethylenehexamine (peha). The tetrahedral [SbSe4]3 − unit connects [Sm(peha)]3 + into the neutral 1-D coordination polymer 1 as a tridentate μ-1κ2:2κ-SbSe4 bridging and chelating ligand. It coordinates to [Eu(peha)]3 + with a 1κ2-SbSe4 chelating mode, forming the mononuclear complex 2. The tridentate μ-1κ2:2κ-SbSe4 bridging and chelating mode and 9-coordinate Sm(III) center in 1 are firstly observed in the systematic syntheses of the Sm/Sb/Se system in different polyethylenediamines. Compounds 1 and 2 exhibit steep band gaps at 2.04 and 2.11 eV at room temperature, respectively.The first lanthanide–tetraselenidoantimonate complexes with hexadentate polyamine co-ligand, [Sm(peha)(SbSe4)]n (1) and [Eu(peha)(SbSe4)] (2) were prepared by solvothermal methods using peha as solvent, and the first μ-1κ2:2κ-SbSe4 ligand to Sm(III) center is observed.Display Omitted
Keywords: Tetraselenidoantimonate ligand; Lanthanide; Hexadentate polyamine; Coordination mode; X-ray structure determination;

A novel Zn6Co3 cluster-based heterometallic coordination polymer, [Zn6Co3(PMG)6(H2O)4]·12H2O (1), has been hydrothermally synthesized, in which the PMG3 − (N-(phosphonomethyl)glycinate) as a multifunctional ligand was firstly formed via in situ decarboxylation from original ligand N-(phosphonomethyl)imino-diacetic acid during the hydrothermal reaction. The complex was characterized by elemental analysis, FT-IR, powder X-ray diffraction, thermal analysis and single-crystal X-ray diffraction techniques. Its structure features a 2D framework constructed by [Zn6Co3(PMG)6(H2O)4] pinwheel-like heteronuclear clusters, which contains rings with two tropisms. Through extensive O–H⋯O hydrogen bondings, the adjacent 2D layered structure further extends into a 3D supramolecular network. Moreover, the solid-state fluorescence property of this complex has also been investigated at room temperature, which exhibits a good fluorescent emission.A novel Zn6Co3 cluster-based heterometallic coordination polymer, [Zn6Co3(PMG)6(H2O)4]·12H2O, was synthesized under hydrothermal conditions, in which PMG3 − ligand was formed via in situ decarboxylation from original ligand H4PMIDA. It features a 2D layer constructed by [Zn6Co3(PMG)6(H2O)4] pinwheel-like heteronuclear clusters, which further extends into a 3D supramolecular network through extensive O–H⋯O hydrogen bonding.Display Omitted
Keywords: Heteronuclear cluster; Phosphonic acid; In situ ligand synthesis; Crystal structure; Fluorescent property;

A fluorescence chemosensor for benzonitrile derived from in-situ synthesis of azolate–carboxylic acid and zinc(II) ions by Ling Li; Ji-Yong Zou; Sheng-Yong You; Yin Hu; Qing-Rong Ji; Kai-Hong Chen; Jian-Zhong Cui (111-114).
A new zinc(II) homometallic coordination polymer (CP), {[Zn(TAA-OH)2] · 1.5H2O} n (1) (HTAA-OH = 2-(5-hydroxy-1H-1,2,4-triazole-1-yl) acetic acid) has been synthesized via an in-situ synthetic approach and structurally characterized in detail. In 1, the HTAA-OH ligand is generated in-situ by the nucleophilic addition of 2-(1H-1,2,4-triazole-1-yl) acetic acid. CP 1 features a 2D structure with sql topology, where the neighboring Zn(II) ions are bridged through two oxygen atoms of carboxyl group and two nitrogen atoms of triazole from the HTAA-OH ligands. Luminescence study shows that 1 dispersed in acetonitrile performs a distinct luminescence enhancing effect upon addition of benzonitrile, indicating that 1 is a promising fluorescence chemosensor for benzonitrile.A 2D sql topological zinc(II) homometallic coordination polymer via an in-situ synthetic approach was synthesized and fully characterized. Luminescence performance reveals that this coordination polymer is a promising fluorescence chemosensor for benzonitrile.Display Omitted
Keywords: In-situ synthesis; HTAA-OH ligand; Zinc coordination polymer; Fluorescence chemosensor;

Assembly of 3-(2-pyridyl)-4-(4-pyridyl)-5-(3-pyridyl)-1,2,4-triazole (L243 ) with Cu(NO3)2 or Cu(ClO4)2 affords a mononuclear complex [Cu(L243 )2(H2O)2](NO3)2 (1) or a 1D linear coordination polymer {[Cu(L243 )2(H2O)](ClO4)2(CH3OH)} n (3). Incorporating NaN3 into such assembled systems under similar conditions will produce two distinct 2D layered networks with the formulas {[Cu(L243 )(N3)](NO3)(H2O)2} n (2) or {[Cu(L243 )(N3)](ClO4)(H2O)} n (4), both of which contain dual inorganic-anions as the counterparts (NO3 /N3 for 2 and ClO4 /N3 for 4). Further, with a subtle change of reaction condition for 2 or 4, a 1D linear array [Cu(L243 )(N3)2] n (5) is obtained with only N3 equilibrating the positive charges. Significantly, stepwise structural transformations between such crystalline phases can also be achieved by the direction of azide anion.A series of Cu(II) supramolecular complexes can be assembled from 3-(2-pyridyl)-4-(4-pyridyl) -5-(3-pyridyl)-1,2,4-triazole and different inorganic salts, in which azide anion is involved as the counterpart in different degrees to regulate their structures and stepwise structural evolution.Display Omitted
Keywords: Coordination assemblies; Anion effect; Tripyridyltriazole ligand; Cu(II) complexes; Structural transformation;

Phenanthroline modulated self-assembly of nano/micro-scaled metal–organic frameworks by Yuhua Zheng; Xun Sun; Huijuan Su; Libo Sun; Qingquan Lin; Caixia Qi (119-121).
In stark contrast to the report that phenanthroline is an efficient chelate ligand for lanthanide-based metal–organic framework formation, here it is found that phenanthroline can act as a very useful regent to modulate self-assembly of nano/micro-sized yttrium benzenetricarboxylate (Y–BTC). 1D nanobelts of Y–BTC was firstly produced via a simple, mild one-step approach. Then the morphology was transformed to 3D urchin-like hierarchical architectures with the assistance of phenanthroline. Interestingly, the as-synthesized 3D urchin-like superstructures can be disassembled through simple ultrasonic treatment. Thus a large quantity of 1D nanorods was obtained. Additionally, brilliant-red light of the nanomaterials was realized by doping Eu3 + ions.3D urchinlike superstructures are realized mediated by phenanthroline while 1D nanobelts of lanthanide-based MOFs were obtained without phenanthroline, indicating that phenanthroline can act as an effective reagent to modulate self-assembly of MOFs.Display Omitted
Keywords: Metal–organic framework; Nanocrystal; Self-assembly; Phenanthroline;

Two layer-like coordination polymers, {[Cd(Bpyen)0.5(m-BDC)(H2O)Br]·4H2O}(1) and {[Cd(Bpyen)0.5(o-BDC)Br]·H2O}(2), have been solvothermally synthesized and structurally characterized. The two compounds own common rapid photochromic response but different decolorization behaviors. The photoproduct of compound 2 is more stable in air. The relationship between structure and photoresponsive behavior has been studied in detail.Two two-dimensional bipyridinium-based coordination polymers have been synthesized, and the structure–property relationship involving photochromism and decolorization has been studied detailedly.Display Omitted
Keywords: Cadmium(II) complex; Bipyridinium; (6,3) topology; Photochromism; Decolorization; Single crystal;

A new paradodecatungstate-B compound decorated by transition metal copper, Na2Cu5(H2O)24(OH)2[H2W12O42]·10H2O (1), has been synthesized by convenient aqueous solution method and structurally characterized by single-crystal X-ray diffraction, IR spectrum, elemental analysis and TGA. The compound crystallizes in the triclinic P-1 space group with a = 10.7140(8) Å, b = 12.9476(9) Å, c = 13.6696(10) Å, α = 73.56°, β = 75.73°, γ = 67.69°, V = 1661.8(2) Å3 and Z = 1. In compound 1, polyanion of [H2W12O42]10 − acts as a dodecadentate ligand that links copper and sodium cations, forming a remarkable three-dimensional framework. The experiment of antitumor activities in vitro shows that the title compound exhibits remarkable inhibitory actions on human cervical carcinoma HeLa cells, ovarian carcinoma SKOV-3 cells, hepatoma HepG2 cells and neuroblastoma SHY5Y cells.Compound 1 consists of [H2W12O42]10 − polyanions linked by copper and sodium cations, forming a remarkable three-dimensional framework. The results of antitumor activities show that 1 has remarkable inhibitory actions on human cervical carcinoma HeLa cells, ovarian carcinoma SKOV-3 cells, hepatoma HepG2 cells and neuroblastoma SHY5Y cells in vitro.Display Omitted
Keywords: Paradodecatungstate-B compound; Crystal structure; Antitumor activity;