Inorganic Chemistry Communications (v.36, #C)

Contents List (iii-xviii).

A new luminescent Zn(II) coordination polymer, namely [Zn4(L)2(μ 4-O)(H2O)2(DMF)]n (1 H3L = biphenyl-3,4,5-tricarboxylic acid, DMF = N,N′-dimethyl formamide) has been synthesized by combining the H3L ligand with Zn(II) salts under solvothermal conditions. Single-crystal X-ray diffraction analysis reveals that 1 features μ 4-oxygen-bridged tetrahedral {Zn4O} clusters as building subunits, which are further bridged by L3 − ligands into a complicated three-dimensional (3D) architecture. Topological analysis reveals that it can be reduced into a (3, 6)-connected topological network with the schläfli symbol of {4 · 62}2{42  · 69  · 84}. In addition, the luminescent property of 1 was also investigated in the solid state at room temperature.Presented here is a new luminescent Zn(II) coordination polymer, namely [Zn4(L)2(μ 4-O)(H2O)2(DMF)]n (1 H3L = biphenyl-3,4,5-tricarboxylic acid, DMF = N,N′-dimethyl formamide), which features a complicated 3D architecture based on isolated tetrahedral {Zn4O} clusters.Display Omitted
Keywords: Zn(II); Solvothermal synthesis; Tetrahedral cluster; Luminescence;

An intriguing 4d–4f heterometallic coordination polymer with 1D pseudo-nanotube architectures by Yi-Fan Kang; Ping Liu; Chao Yuan; Lin Cui; Yang Liu; Yao-Yu Wang (4-7).
A new one-dimensional (1D) 4d–4f heterometallic coordination polymer [ErAg(Himdc)2(H2O)3] (1) (H3imdc = 4,5-imidazoledicarboxylic acid) is synthesized under hydrothermal condition and characterized by elemental analysis, IR, PXRD and single crystal X-ray diffraction. Complex 1 crystallizes in the triclinic space group P-1, showing a 1D metal–organic pseudo-nanotube with a 4.014 × 12.027 Å2 cross-section. Furthermore, it assembles into a 3D supramolecular architecture via hydrogen bonds between pseudo-nanotubes. The complex 1 exhibits solid-state photoluminescence and high thermal stability.A 4d–4f heterometallic complex is synthesized and characterized by elemental analysis, IR, PXRD and single crystal X-ray diffraction. Complex 1 shows a metal–organic pseudo-nanotube with a 4.014×12.027 Å2 cross-section. Furthermore, it assembles into a 3D supramolecular architecture via hydrogen bonds. The complex 1 exhibits luminescence and high thermal stability.Display Omitted
Keywords: Heterometallic; Coordination polymer; Pseudo-nanotube; Luminescence;

The structure of [Ag(dmso)BF4] is described, in which the tetrafluoroborate ion is only weakly coordinated. A corrugated sheet structure is formed by self-assembly of the [Ag(dmso)]+ building blocks through triply bridging μ3-S,O,O-dmso ligands. This is a new bonding mode for transition metals with sulfoxide ligands and suggests that self-assembly of complex structures from sulfoxide ligands is a field with significant potential.The first example of a triply bridging μ3-S,O,O-dmso ligand is found in the structure of [{Ag(dmso)}n]+, which forms a new corrugated sheet structure by self-assembly.Display Omitted
Keywords: Silver; Dimethylsulfoxide; Self-assembly;

Hetero-trinuclear near-infrared (NIR) luminescent ZnLn2 (Ln = Nd, Yb or Er) complexes based on monomer ZnL Schiff-base precursor and o-vanillin by Zheng Wang; Weixu Feng; Peiyang Su; Han Liu; Zhao Zhang; Yao Zhang; Tiezheng Miao; Xingqiang Lü; Daidi Fang; Wai-Kwok Wong; Richard A. Jones (11-13).
With the monomer [Zn(L1)(H2O)] (1) complex in situ formed by the deprotonated hexadentate Salen-type Schiff-base ligand H2L1 (H2L1  = N,N′-bis(3-methoxy-salicylidene)cyclohexane-1,2-diamine) and Zn(NO3)2 as the precursor, series of the hetero-trinuclear ZnLn2 complexes [ZnLn2(L1)2(L2)(NO3)2Cl] (Ln = Nd, 2; Ln = Yb, 3; Ln = Er, 4 or Ln = Gd, 5) were obtained from the further reaction with LnCl3 (Ln = Nd, Yb Er or Gd) and the second o-vanillin (HL2 ) ligand, respectively. The photophysical properties of complexes 24 showed that the characteristic near-infrared (NIR) luminescence of Ln3 + ions with two emission centers and emissive lifetimes in microsecond ranges, was sensitized from the excited state (both 1LC and 3LC) of mixed H2L1 HL2 ligands.As to the obtained complexes [ZnLn2(L1)2(L2)(NO3)2Cl] Ln = Nd, 2; Yb, 3; Er, 4 or Gd, 5), the result of their photophysical properties shows that the characteristic NIR emission of Ln3+ ions for 2-4 with two luminescent centers and emissive lifetimes in microsecond ranges.Display Omitted
Keywords: Hetero-trinuclear ZnLn2-arrayed complexes; Mixed H2L1 HL2 ligands; Sensitization of NIR luminescence;

Distinctly selective reactions of based on acetate lead(II) and hydrophilic 3-(4-carboxyphenoxy)phthalic acid by Jun Chen; Lei Hou; Wen-Huan Huang; Wei-Ping Wu; Cui-Ping Zhang; Yao-Yu Wang; Qi-Zhen Shi (14-17).
Exceptional 3D Pb(II) MOFs constructed by Pb5(II) cluster motifs have been obtained by hydrothermal reaction of hydrophilic 3-(4-carboxyphenoxy)phthalic acid (H3L) and acetate lead in aqueous solution. Specifically, in this system, an obvious selective reaction of Pb(OAC)2 and H3L has been found. No matter the N-containing heterocyclic auxiliary ligands exist or not, the same products without auxiliary ligand are generated. Moreover, the luminescent property of 1 has also been investigated.A exceptional 3D MOFs constructed by Pb5(II) cluster motifs have been obtained by hydrothermal reaction of hydrophilic 3-(4-carboxyphenoxy)phthalic acid (H3L) and acetate lead in aqueous solution. Specifically, in this system, an obvious selective reaction of Pb(OAC)2 and H3L has been found. Moreover, the luminescent property of 1 has been investigated.Display Omitted
Keywords: 3-(4-Carboxyphenoxy)phthalic acid; Selective reactions; Hydrophilic;

A series of bimetallic chain coordination polymers bearing [Ag(PPh3)2] chromophores: Synthesis, structure and luminescence by Mohamed Ghazzali; Mohammed H. Jaafar; Sebastiaan Akerboom; Ali Alsalme; Khalid Al-Farhan; Jan Reedijk (18-21).
A series of three cyanide-bridged chain coordination compounds with the formulae [M(CN)2(PPh3)2Ag] n (M is Ag, Cu or Au) is presented. The compounds have been prepared by room temperature reactions of triphenylphosphane with the cyanide salts of silver(I), copper(I) and gold(I). The compounds are characterised with IR, elemental analyses, SEM-EDX and X-ray powder diffraction, and the molecular structures were elucidated by single crystal X-ray diffraction. The three compounds are best described as one-dimensional cyanide-bridged chain coordination polymers, where the tetrahedral AgI ions are coordinated by 2 triphenylphosphane ligands and 2 cyanides, forming a AgN2P2 chromophore. The linear Ag(I), Cu(I) and Au(I) centers are in two-coordinate geometry with C-bound cyanides. No aurophilic or argentophilic interactions are observed, but in the lattice only C-H…π and C-H…M hydrogen bonds are present. The solid-state luminescence properties of the three compounds are discussed and assigned, in agreement with DFT calculations, to MMLCT.Three cyanide-bridged univalent coinage metal polymeric chain compounds of the formulae [M(C = N)2(PPh3)2Ag] n are presented and its solid-state photoluminescence electronic transitions are attributed to MMLCT.Display Omitted
Keywords: Bimetallic; Coordination polymers; Luminescence; Single crystal diffraction; Coinage metals;

The first substituted macrocyclic ligand Py2N4S2 containing four naphthylmethylene pendant-armed groups: Synthesis and photophysical properties by Verónica García; Anxela Aldrey; Catherine S. De Castro; Rufina Bastida; Alejandro Macías; Carlos Lodeiro; J. Sérgio Seixas de Melo; Cristina Núñez (22-26).
The synthesis of a pendant donor emissive macrocyclic ligand Py2N4S2 with up to four naphthylmethylene arms (L) has been achieved. Their derivative solid metal complexes (Co2 +, Ni2 +, Cu2 +, Zn2 +, Cd2 +, Hg2 + and Ag+) have been isolated and characterized. The photophysical properties of the free ligand L and their complexation behaviour have been investigated in solution. In dichloromethane, the free ligand presents two emission bands which are related to the monomer naphthalene emission and a red-shifted band attributable to ground state dimers (interaction between two naphthalene chromophores), which was further validated from time-resolved data, with bi-exponential decay with absence of dynamic components. UV–Vis spectroscopy has revealed a 2:1 binding stoichiometry for Co2 +, Cu2 +, Zn2 +, Hg2 + and Ag+.Synthesis of a novel emissive macrocyclic ligand L containing four naphthylmethylene arms and their derivative solid metal complexes (Co2 +, Ni2 +, Cu2 +, Zn2 +, Cd2 +, Hg2 + and Ag+).The photophysical properties of the free ligand L and their complexation behaviour have been investigated in organic solution.Display Omitted
Keywords: Macrocycles; Dinuclear complex; Stability constant; Naphthalene; Pendant-arms; Sensor;

A new hybrid zinc phosphite with a pillared layered structure: Synthesis and characterization of [C6N2O2H16][Zn(HPO3)]2 by Guo-Ming Wang; Xiao Zhang; Jin-Hua Li; Zong-Hua Wang; Ying-Xia Wang; Jian-Hua Lin (27-30).
By using flexible 1,2-bis(2-aminoethoxy)ethane (BAEOE) as a pillaring ligand, a new inorganic–organic hybrid open-framework zinc phosphite, [C6N2O2H16][Zn(HPO3)]2 (1), has been hydrothermally synthesized and structurally characterized by IR, elemental analysis, thermogravimetric analysis, powder and single-crystal X-ray diffractions. The structure of 1 consists of neutral layers of zinc phosphite which are further pillared through linear BAEOE ligands, generating a 3D framework with unusual (3, 4)-connected dmc topology. The participation of left-handed and right-handed helical chains in the construction of puckered sheet structure with 4.82-net is also noteworthy.A new inorganic–organic hybrid zinc phosphite, [C6N2O2H16][Zn(HPO3)]2 (1), has been synthesized under hydrothermal conditions. The structure consists of neutral layers of zinc phosphite which are further pillared through linear BAEOE ligands, generating a 3D framework with unusual (3, 4)-connected dmc topology. It is the first 3D inorganic–organic hybrid metal phosphite pillared by flexible aliphatic polyamines.Display Omitted
Keywords: Zinc phosphite; Hybrid material; Hydrothermal synthesis; Helical chains; Crystal structure;

Two novel Er(III) metal–organic frameworks, namely, {[Er5(bptc)3(Hbptc)(H2O)12]·4H2O} n (1) and {[Er(bptc′)]} n (2) have been synthesized through the hydrothermal reaction of H4bptc with trivalent erbium salts in different temperatures (H4bptc = 2,2′-bipyridine-3,3′,6,6′-tetracarboxylic acid, H3bptc′ = 2,2′-bipyridine-3,6,6′-tricarboxylic acid). The hydrothermal decarboxylation of H4bptc into H3bptc′ in 2 was found in higher temperature. Compound 1 reveals a 2-D layered structure and 2 exhibits a 3-D framework structure. The near-infrared luminescent properties of compounds 12 have been investigated at 77 K.Compound 1 reveals a 2-D layered structure and 2 exhibits a 3-D framework structure.Display Omitted
Keywords: Coordination Polymer; Crystal Structure; Near-Infrared Luminescence;

A terpyridine ligand encompassing a terminal 4-carboxyphenyl group (cptpy), was employed in a new Ru(II) black dye, in the presence of 8-quinolinolate (Q) and SCN as ancillary ligands. Such compound, here referred as [Ru(cptpy) (Q) (NCS)], was designed aiming its inclusion into carboxymethyl-beta-cyclodextrin, anchored on TiO2. This host–guest strategy was employed to prevent the formation of aggregates and protect the photoinjecting moiety against parallel deactivation events. Such expectation has indeed been fulfilled by the system. On the other hand, 8-quinolinolate as a strong electron donor ligand, effectively enhanced the light harvesting behavior of the dye, shifting and spreading the IPCE peaks over the entire visible region. Unfortunately, the red shift of visible charge-transfer bands was compensated by a decrease of the Ru(III)/(II) potentials, slowing down the electron transfer kinetics with the I3/I redox mediator. Therefore, the observed counterbalance between charge transfer energies and redox potentials imposes a critical limit in the design of better mononuclear ruthenium-polypyridine dyes.Improved light harvesting performance and host–guest protection were pursued by using a ruthenium(II) dye with carboxyphenylterpyridine and 8-hydroxyquinoline ligands.Display Omitted
Keywords: Ruthenium polypyridines; DSSC; Solar cell; Cyclodextrin; Titanium dioxide;

New dimeric phosphine ylide copper (I) complexes: Synthesis, coordination behavior, and application in Suzuki cross-coupling reactions by Seyyed Javad Sabounchei; Mahbubeh Pourshahbaz; Mohsen Ahmadi; Ali Hashemi; Hamid Reza Khavasi (39-44).
The reaction of the non-symmetric phosphorus ylides, Ph2P(CH2)nPPh2C(H)C(O)PhR with CuCl in equimolar ratios using dry methanol as solvent give binuclear complexes of the type [Cu(μ-Cl){Ph2P(CH2)nPPh2C(H)C(O)PhR}]2 (n  = 1: R = Br (1), OCH3 (2); n  = 2: R = Br (3), OCH3 (4)). X-ray analyses of 1 demonstrate the Cl bridged dimeric structures with P,C-chelated ligands. Characterizations of these compounds were carried out by FT-IR and multinuclear NMR technique. Elemental analysis indicate a 1:1 stoichiometry between the ylides and the Cu(I) chloride in the four complexes. The precursor complexes 1 and 3 are found to exhibit high catalytic activity in the Cu-catalyzed Suzuki cross-coupling reactions in an air atmosphere at medium catalyst loading in DMF as a solvent. The use of 5 mol% catalyst in the presence of Cs2CO3 allows the coupling reaction to proceed with moderate to excellent yields.The reactions of CuCl with bidentate α-keto stabilized phosphorus ylides give binuclear complexes of the type [Cu(μ-Cl){ Ph2P(CH2)nPPh2C(H)C(O)PhR}]2 (n  = 1: R = Br (1), OCH3 (2), n  = 2: R = Br (3), and OCH3 (4)). X-ray analysis of 1 demonstrates a Cl bridged dimeric structure with P,C-chelated ligands. Highly efficient Suzuki cross-coupling reaction between various aryl halides and phenylboronic acid using 1 and 3 as catalyst precursors under aerobic conditions has been developed.Display Omitted
Keywords: Phosphorus ylide; Cu(I) complex; X-ray crystal structure; Suzuki cross-coupling reaction; High catalytic activity; Copper-catalyzed;

Four novel DNA metalloinsertors having imino-oxalato mixed-ligands, of the composition [ML(ox)]Cl2 (where M = Cu(II), Co(II), Ni(II) and Zn(II); ox = C2O4 2 − and L = N,N′-bis(4-chlorobenzylidene)benzene-1,2-diamine) were synthesized. They were fully characterized by microanalytical data, magnetic susceptibility values, molar conductivity measurements, UV–vis, IR, 1H NMR, 13C NMR and EPR techniques. Their geometry was explored and found to have square-planar geometry. Electronic absorption spectroscopy, cyclic voltammetry and viscosity measurements indicate that these mixed-ligand complexes strongly bind to calf thymus DNA, presumably via an intercalation mechanism. Further, DNA cleavage efficacy of these complexes was investigated by gel electrophoresis. The complexes were found to promote the cleavage of pBR322 DNA in the presence of the reluctant, ascorbic acid. The ligand (L) and the mixed-ligand complexes were tested for their efficiency towards antimicrobial activity and their MIC data reveal that all the complexes have strong activity in comparison to the free ligand and standard drugs, ciprofloxacin and fluconazole.The synthesized efficient intercalating mixed ligand metal complexes are valuable in designing novel agents for targeting nucleic acids as well as setting the stage for the synthesis of metal nuclease drugs.Display Omitted
Keywords: Mixed-ligand complexes; Calf thymus DNA; Intercalation; pBR322 DNA; MIC data;

Assembly of 1D and 2D zinc(II) coordination polymers from flexible polyimidazolyl-based ligands by Wen-Yan Yan; Run-Tian He; Min Dai; Zhi-Gang Ren; Hong-Xi Li; Jian-Ping Lang (51-55).
Reactions of Zn(NO3)2∙ 6H2O with 1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene (titmb) in the presence of 1,4-benzenedicarboxylic acid (1,4-H2BDC) or 1,3-benzenedicarboxylic acid (1,3-H2BDC) under hydrothermal conditions afforded one 1D and one 2D coordination polymers [Zn3(titmb)2(1,4-BDC)3(H2O)6] (1) and [Zn2(titmb)(1,3-BDC)2(H2O)] (2), respectively. Similar reactions of Zn(NO3)2∙ 6H2O with 1,3-bis(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene (bitmb) and 1,4-H2BDC gave rise to one 2D coordination polymer [Zn2(bitmb)2(1,4-BDC)2] (3). Compound 1 has a 1D linear chain formed from linking 24-membered [Zn2(titmb)2] metallamacrocycles and [Zn(1,4-BDC)(H2O)2] units via imidazolyl groups of titmb ligands. Compound 2 has a 2D network assembled from connecting spiral [Zn n (1,3-BDC) n ] chains with titmb linkers, while compound 3 also has a 2D network formed by linking 24-membered [Zn2(bitmb)2] metallamacrocycles via 1,3-BDC bridges. The ligands titmb and bitmb in compounds 13 adopt less-common cistranstrans and cistrans conformations, respectively. Their thermal and photoluminescent properties were also investigated.Three Zn(II) coordination polymers [Zn3(titmb)2(1,4-BDC)3(H2O)6] and [Zn2(titmb)(1,3-BDC)2(H2O)], [Zn2(bitmb)2(1,4-BDC)2] were generated from hydrothermal reactions of Zn(NO3)2∙ 6H2O with 1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene (titmb) or 1,3-bis(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene (bitmb) and 1,4-benzenedicarboxylic acid (1,4-H2BDC) or 1,3-benzenedicarboxylic acid (1,3-H2BDC). These complexes were structurally characterized by elemental analysis, IR, and X-ray crystallography and their thermal and luminescent properties were studied.Display Omitted
Keywords: Zinc; Coordination polymer; 1,3,5-Tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene; 1,3-Bis(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene; Hydrothermal synthesis;

Chiral heterometallic 3d–3d azido complex: Synthesis, structure and magnetic properties by Yong-Kun Jiao; Xiu-Ping Li; Cui Zhao; Jiong-Peng Zhao; Fu-Chen Liu (56-58).
A novel three-dimensional chiral heterometallic 3d–3d azido complex, [Co2Zn(N3)4(pyzc)2](1) (pyzc = 2-pyrazinecarboxylate), was obtained by assembling CoII, ZnII, azido, and pyrazine carboxylate under solvothermal condition. The structure of the complex can be described as end-on (EO) azido, end-to-end (EE) azido mixed bridged alternate Co–Zn chains linked by the 2-pyrazinecarboxylate. Magnetic studies indicate that dominant anti-ferromagnetic coupling interactions exist in the complex.A novel three-dimensional chiral heterometallic 3d–3d azido complex [Co2Zn(N3)4(pyzc)2](1) (pyzc = 2-pyrazinecarboxylic acid) has been synthesized under solvothermal condition and exhibits interesting structure and magnetic properties.Display Omitted
Keywords: Metal–azido; Heterometallic; Chiral; Solvothermal reaction; Magnetic properties;

Two-dimensional Mn(II) and Cd(II) networks with tetrazole-containing ligand and their properties by Gao-Chao Lv; Yue Zhao; Jian Fan; Shui-Sheng Chen; Zhi Su; Wei-Yin Sun (59-62).
Three new Mn(II) and Cd(II) coordination polymers with kgd network topology, namely, [Mn3(T4)2(DEF)6] · 2H2O (1), [Mn3(T4)2(DMSO)2(CH3OH)4] · 2CH3OH · 3H2O (2) and [Cd3(T4)2(DMF)6] · 5CH3OH · 3DMF · H2O (3), have been prepared by reactions of tris[4-(1H-tetrazol-5-yl)phenyl]amine (H3T4) with corresponding metal salt and characterized by single crystal and powder X-ray diffractions, IR and thermogravimetric analyses. In compounds 1 and 3, the layers adopt center to center stacking, while there is a slight shifting between the adjacent layers in compound 2. Complexes 1 and 2 exhibit overall weak antiferromagnetic coupling between the neighboring Mn(II) atoms, and compound 3 shows luminescent property in the solid state at room temperature.Three new Mn(II) and Cd(II) coordination networks with kgd topology, namely, [Mn3(T4)2(DEF)6] · 2H2O (1), [Mn3(T4)2(DMSO)2(CH3OH)4] · 2CH3OH · 3H2O (2) and [Cd3(T4)2(DMF)6] · 5CH3OH · 3DMF · H2O (3), have been prepared by reactions of tris[4-(1H-tetrazol-5-yl)phenyl]amine (H3T4) with corresponding metal salt and characterized.Display Omitted
Keywords: Mn(II) and Cd(II) complexes; kgd net; Crystal structure; Fluorescence property; Antiferromagnetic coupling;

The hydrothermal reactions of D(+)-camphoric acid (D-H2Cam) and 1,10-phenanthroline (phen)/2,2′-bipyridine (2,2′-bipy) with the corresponding metal salts gave rise to eleven chiral 3d–4f heterometallic metal-organic frameworks (MOFs). Single-crystal X-ray diffraction measurements reveal that the crystal structures are isostructural, crystallizing in the orthorhombic space group P212121 and they exhibit unique three-dimensional chiral 6-connected frameworks involving 1D zigzag chains aligned parallel to the a axis and the 2D wave-like lanthanide layers, with the Schläfli symbol (49  · 66). Moreover, we have systematically investigated the magnetic behaviors of partial compounds.Eleven chiral 3d-4f Metal-Organic Frameworks constructed from D(+)-camphoric acid have been synthesized. The crystal structures exhibit unique three-dimensional chiral 6-connected frameworks. The magnetic behaviors have been systematically investigated.Display Omitted
Keywords: Crystal structures; Chiral MOFs; 3d–4f complexes; Magnetic properties;

Synthesis, crystal structure and antimicrobial studies of a thione derivative of transplatin, trans-[Pt(NH3)2(Diaz)2]Cl2·2H2O (Diaz = 1,3-diazinane-2-thione) by Seerat-ur-Rehman; Anvarhusein A. Isab; Muhammad Nawaz Tahir; Tanzeel Khalid; Muhammad Saleem; Haseeba Sadaf; Saeed Ahmad (68-71).
Platinum(II) complexes, trans-[Pt(NH3)2(Diaz)2]Cl2·2H2O (1) and trans-[Pt(NH3)2(Tu)2]Cl2 (Diaz = 1,3-diazinane-2-thione, Tu = thiourea) were prepared and characterized by elemental analysis, IR and NMR spectroscopy. The crystal structure of compound 1 was determined by X-ray crystallography. The structure of 1 consists of trans-[Pt(NH3)2(Diaz)2]2 + cation, two chloride ions and two water molecules. In trans-[Pt(NH3)2(Diaz)2]2 +, the geometry at platinum is nearly regular square planar with the average cis and trans angles of 90° and 180° respectively. The 1H and 13C NMR spectral data indicated the coordination of both ligands to platinum(II). Antimicrobial activities of the complexes were evaluated by minimum inhibitory concentration and the results showed that the complexes exhibited significant activities against gram-negative bacteria (Escherichia coli, Pseudomonas aeruginosa). However, moderate activity was observed against molds (Aspergillus niger, Penicillium citrinum).Platinum(II) complexes, trans-[Pt(NH3)2(Diaz)2]Cl2·2H2O (1) and trans-[Pt(NH3)2(Tu)2]Cl2 (Diaz = 1,3-diazinane-2-thione, Tu = thiourea) were prepared and characterized by elemental analysis, IR and NMR spectroscopy. The structure of 1 consists of trans-[Pt(NH3)2(Diaz)2]2 + cation, two chloride ions and two water molecules. Antimicrobial activities of the complexes were evaluated by minimum inhibitory concentration and the results showed that the complexes exhibited significant activities against gram-negative bacteria and molds.Display Omitted
Keywords: Platinum(II) complexes; Transplatin; 1,3-Diazinane-2-thione; Thiourea; X-ray structure;

Turn-on selective fluorescent probe for trivalent cations by Hyun Kim; Kyung Beom Kim; Eun Joo Song; In Hong Hwang; Jin Young Noh; Pan-Gi Kim; Kwang-Duk Jeong; Cheal Kim (72-76).
A novel fluorescent sensor 1 (1  = 10-(2-(((pyridin-2-yl)methylamino)methyl)phenol)methyl-anthracene) for trivalent cations has been synthesized and characterized. Both UV-vis and fluorescence spectroscopic studies demonstrated that the new receptor 1 was highly sensitive and selective toward trivalent cations, while there was no response to monovalent and divalent cations in methanol. Upon binding with trivalent cations, the emission bands of 1 red-shifted for all the trivalent cations from 411 nm to 421 nm and their fluorescence intensities were enhanced. In particular, Fe3 + could be obviously discriminated from Fe2 +. The binding modes of 1 and the trivalent cations (M3 + ions) were found to be 1:1 and confirmed by Job plot, 1H NMR titration and ESI-mass spectrometry analysis.A novel fluorescent sensor 1 (1  = 10-(2-(((pyridin-2-yl)methylamino)methyl)phenol)methyl-anthracene) has been synthesized and characterized. Upon binding with trivalent cations, the emission bands of 1 red-shifted for all the trivalent cations from 411 nm to 421 nm and their fluorescence intensities were enhanced. In particular, Fe3+ could be obviously discriminated from Fe2+.Display Omitted
Keywords: Trivalent cations; Pearson's principle; Fluorescent probe; PET process;

The interaction between meso-tetraarylporphyrinato magnesium(ІІ) [MgT(4-X)PP] (X = H, CH3, and CH(CH3)2) and PCl3, as an electron acceptor, produced new molecular complexation [MgT(4-X)PP(PCl3)2]. The synthesized molecular complexes were characterized by (1H, 31P) NMR, UV–Vis, FT-IR spectroscopies and electric conductivity. In these molecular complexes, the central core of porphyrin, corrugates and two lone electron pairs of nitrogen atoms in the metalloporphyrin act as σ-electron donors to a phosphorous atom in PCl3 and the second PCl3 molecule acts as a ligand to magnesium(II) ion. The molar ratio of metalloporphyrin to PCl3 in the molecular complexes was 1:2. The synthesized molecular complexes in acetone solvent showed no electric conductivity.The interaction between meso-tetraarylporphyrinato magnesium(ІІ) [MgT(4-X)PP] (X = H, CH3, and CH(CH3)2) and PCl3, as an electron acceptor, produced new molecular complex [MgT(4-X)PP(PCl3)2], with the molar ratio of 1:2 (donor:acceptor).Display Omitted
Keywords: Molecular complex; Metalloporphyrin; PCl3; Donor; Acceptor; Deformation;

Two isostructural 3D metal–organic frameworks constructed from 1D [H2Mo4O14]n 2n − chains and the flexible bis-pyridyl-bis-amide ligand by Hongyan Lin; Chuang Xu; Xiuli Wang; Zhihan Chang; Aixiang Tian; Guocheng Liu; Juwen Zhang (81-85).
Two new isostructural metal–organic frameworks based on 1D [H2Mo4O14]n 2n − chains and the flexible N,N′-bis(3-pyridinecarboxamide)-1,2-ethane (L), [M(L)(H2Mo4O14)(H2O)2] (M = CoII for 1, NiII for 2), have been hydrothermally synthesized and characterized by single crystal X-ray diffraction. In the title complexes, the unusual 1D [H2Mo4O14]n 2n − chains are linked by the MII ions to form a 2D inorganic bimetallic layer. The adjacent 2D layers are further connected by the L ligands to construct a 3D framework with CdSO4 topology. The electrochemical behaviors and the photocatalytic activities of the title complexes have been investigated.By introducing the flexible N,N′-bis(3-pyridinecarboxamide)-1,2-ethane (L) in the polyoxometalate (POM) system, two new 3D POM-based metal–organic frameworks with CdSO4 topology were obtained, which represents the first example of POM-based complexes containing the unusual 1D polyoxomolybdate [H2Mo4O14]n 2n − anion chains and flexible bis-pyridyl-bis-amide ligands. The title complexes show good electrochemical properties and dominant photocatalytic activities.Display Omitted
Keywords: Polyoxomolybdate; Flexible bis-pyridyl-bis-amide ligand; Metal–organic framework; Property;

Self-assembly of CoSO4 salt and 2-(p-isopropylphenyl)-1H-imidazole-4,5-dicarboxylic acid (H3PPhIDC), results in the formation of a metal-organic framework, [Co(HPPhIDC)(CH3OH)] n (1), which has been characterized by elemental analysis, IR, X-ray powder diffraction (XRPD), thermogravimetric analysis and single-crystal X-ray diffraction. Polymer 1 is a meso-compound and displays a (3,3)-connected 3D structure with 1D channels and cages, which are composed of left- and right-handed helices pillared by Co2 + linkers. Moreover, the antiferromagnetic coupling between the neighboring Co(II) ions in 1 can be observed.One three-dimensional Co(II) imidazole dicarboxylate-based polymer has been solvothermally prepared and structurally characterized by single-crystal X-ray crystallography. The thermal and magnetic properties of the polymer have been investigated.Display Omitted
Keywords: Imidazole dicarboxylate; Cobalt; Polymer; Crystal structure; Property;

Four calcium complexes coordinated with N,N,O-tridentated pyrazolonate (12) or Schiff base (34) ligands have been prepared. These reactions can be monitored by 1H NMR spectroscopic studies with the chemical shift from 2.20 to 2.36 ppm for 1, and 2.22 to 2.28 ppm for 2 for the NMe2 group and the proton peak of the imino group shifted from 8.23 ppm to 7.95 ppm for 3, and 8.52 ppm to 8.14 ppm for 4. Single crystal X-ray studies reveal that complex 1 bears a mononuclear feature with a hexa-coordinated calcium metal center bonded to two NNO-tridentate ligands. Variable temperature dependent 1H NMR spectroscopic studies of 3 indicate that the nitrogen atom of NMe2 group dissociates slowly in solution ranging from − 20 to 80 °C. In the presence of alcohol, all of these complexes show good catalytic activity toward ring-opening polymerization of L-lactide in a well-controlled manner, yielding polymers with expected molecular weights and narrow polydispersity indexes. The activity of these complexes is affected by the basicity of donor atoms.A series of calcium complexes supported by pyrozolonate and Schiff base ligands were synthesized and fully characterized. All of these complexes show efficient catalytic activity toward ring-opening polymerization of L-lactide in the presence of benzyl alcohol.Display Omitted
Keywords: Calcium; Catalyst; Schiff base; Pyrazolonate; Ring-opening polymerization; L-lactide;

L-cysteine recognition triggered by Zn2 + complexation with ligand by Min Joung Kim; Hemant Sharma; Narinder Singh; Doo Ok Jang (96-99).
A new type of benzimidazole-based imine-linked fluorescence chemosensor for Zn2 + was synthesized. Coordination of Zn2 + with the receptor led to enhanced fluorescence while other metals quenched the receptor fluorescence. The resulting complex had a supramolecular assembly with a 1:1 host-guest ratio with variable size. The (1.Zn2 +)n assembly showed high selectivity towards the complexation of L-cysteine even in the presence of other potentially competitive biologically important anionic species.Display Omitted
Keywords: Chemosensor; Molecular recognition; Supramolecular assembly; L-cyteine; Zn(II);

A new quinoline derivatized thiosemicarbazone (1) was designed and synthesized as a colorimetric and fluorescent sensor. Sensor 1 displays highly selective and sensitive recognition to Cu2 + in aqueous solution (1‰ DMSO, HEPES 20 mM, pH = 7.4) via significant color and fluorescence changes. The on-site generated 1-Cu2 + complex exhibits high selectivity toward S2 − over other anions and thiol-containing amino acids. The Cu2 + and S2 − recognition processes are quick and reversible. Thus, rapid and highly selective relay recognition of Cu2 + and S2 − by sensor 1 in aqueous solution has been achieved.A new quinoline derivatized thiosemicarbazone (1) that displays highly selective and sensitive relay recognition to Cu2 + and S2 − in aqueous solution (1‰ DMSO, HEPES 20 mM, pH = 7.4) has been achieved.Display Omitted
Keywords: Copper detection; Sulfide recognition; Fluorescence; Thiosemicarbazide;

Two distinct Co(II) coordination polymers [Co(L-Br)2(H2O)2] n (1) and {[Co(L-Br)2(H2O)0.5](H2O)0.5} n (2) have been prepared from 5-bromonicotinic acid (HL-Br) by using different synthetic approaches (ambient condition vs hydrothermal method). Both complexes have been characterized by elemental analysis, IR, and powder X-ray diffraction. Single crystal X-ray diffraction reveals that 1 displays a 2-D (4,4) polymeric layered network whereas 2 presents a 3-D unusual binodal (3,6)-connected net of (3.4.5)(32.44.55.62.72) topology. Their structural divergences should be properly attributed to the different coordination patterns of L-Br and water ligands. In addition, thermal stability and magnetic properties of both complexes are also studied.Two distinct 2-D and 3-D CoII coordination polymers with 5-bromonicotinate ligand have been obtained from different synthetic approaches (ambient condition vs hydrothermal method), the thermal and magnetic properties of which are also presented.Display Omitted
Keywords: Coordination polymer; Synthetic approach; 5-Bromonicotinic acid; Structural diversity; Network topology;

Synthesis of a polynuclear complex possessing four spatially arranged rhenium units by Bhaskaran Shankar; Palani Elumalai; Malaichamy Sathiyendiran (109-112).
The reaction of Re2(CO)10 with 2-(benzoxazol-2-yl)phenol (HL) and 1,2,4,5-tetrakis(4-pyridylvinyl)benzene (L2) gives a heteroleptic tetranuclear complex, [((fac-Re(CO)3)L)4(L2)] 1. The corner of 1 comprises four spatially arranged mononuclear units.The reaction of Re2(CO)10 with 2-(benzoxazol-2-yl)phenol (H2L) and 1,2,4,5-tetrakis(4-pyridylvinyl)benzene (L2) gives a heteroleptic tetranuclear complex, [((fac-Re(CO)3)L)4(L2)] 1. The corner of 1 comprises four spatially arranged mononuclear units.Display Omitted
Keywords: 2-(Benzoxazol-2-yl)phenol; Mononuclear; Polynuclear complex; Pyridyl donor; Rhenium;

The dications of meso-tetraphenylporphyrin, H2TPP, meso-tetra(4-Cl)phenylporphyrin, H2T(4-Cl)PP and meso-tetra(4-OCH3phenyl)porphyrin, H2T(4-OCH3)PP with formic acid as a weak carboxylic acid have been studied by UV–vis and variable temperature 1H NMR spectroscopies. As would be expected in the presence of a strongly basic counter anion, the formation of very strong N–H–O hydrogen bonds between the diprotonated species and the formate anion leads to considerable broadening of the NH resonance of H2T(4-OCH3)PP(HCOOH)2, H2T(4-Cl)PP(HCOOH)2 and H2TPP(HCOOH)2, so that the signal cannot be observed at or close to room temperatures, but appears at 0 °C for H2T(4-OCH3)PP(HCOOH)2 and at − 30 °C for the latter dications. While the signal of the β protons of H2TPP(HCOOH)2 moves continuously upfield from 20 to − 60 °C, the corresponding signal of H2T(4-OCH3)PP(HCOOH)2 and H2T(4-Cl)PP(HCOOH)2 moves upfield at higher temperatures and downfield at lower temperatures, corresponding to a decrease followed by an increase in the porphyrin ring current.Variable-temperature 1H NMR spectroscopy was performed in the range − 60 to 20 °C to study the diprotonated species of meso-tetraarylporphyrins (aryl = phenyl, 4-methoxylphenyl and 4-chlorophenyl) with formic acid as a weak carboxylic acid.Display Omitted
Keywords: Variable temperature 1H NMR; Porphyrin diacids; Formic acid; Meso-tetraarylporphyrins; Hydrogen bond;

New hydroxylamine-containing macrobicyclic encapsulating ligand: Unexpected double addition of ethyl radicals to the azomethine fragment of a boron-capped iron(II) clathrochelate dioximate by Alexey B. Burdukov; Mikhail A. Vershinin; Evgenii G. Boguslavsky; Ilya V. Eltsov; Galina V. Romanenko; Alexander S. Belov; Yan Z. Voloshin (117-121).
The reaction of the fluoroboron-capped mixed dimethylglyoximate-α-benzyldioximate iron(II) clathrochelate with (C2H5)3B–O2 system as a “soft” radical source afforded the major macrobicyclic product of the reductive addition of two carbon-centered radicals to the azomethine moiety of the dimethylglyoximate fragment giving the chelate ribbed entity that contains both the oxime and hydroxylamine donor groups. Such an unprecedented cage complex of this new encapsulating ligand was thoroughly characterized both in a solution by one- and two-dimensional NMR and in a solid state using X-ray crystallography.The reaction of the mixed dimethylglyoximate-α-benzyldioximate iron(II) clathrochelate with (C2H5)3B–O2 system as “soft” radical source afforded the major macrobicyclic product of reductive addition of two carbon-centered radicals containing both the oxime and hydroxylamine donor groups. This cage complex of new encapsulating ligand was characterized by XRD and solution NMR.Display Omitted
Keywords: Macrocyclic compounds; Clathrochelates; Iron complexes; Ligand reactivity; Radical reactions;

Construction of Co(II) coordination polymers with flexible carboxylate ligands: structural and magnetic studies by Na Xu; Xiao-Hang Qiu; Chao Wang; Jinkui Tang; Peng Cheng; Dai-Zheng Liao (122-125).
Two Co(II) coordination polymers [Co(3-pmna)2(H2O)2] n (1) and {[Co2(4-pmna)4(H2O)]∙0.25H2O} n (2), where 3-Hpmna = 2-(3-pyridylmethylthio)nicotinic acid and 4-Hpmna = 2-(4-pyridylmethylthio)nicotinic acid, were synthesized and fully characterized. 1 displays chain structure, while 2 exhibits 3D coordination network composed of dimer units. Magnetic studies reveal spin-canting behaviors in 1.Two Co(II) coordination polymers were synthesized and characterized crystallographically and magnetically. 1 displays 1D chain structure, while 2 exhibits 3D coordination network composed of dimer units. Magnetic studies reveal antiferromagnetic interaction between the central metal ions in these two compounds, as well as the spin-canting behaviors in 1.Display Omitted
Keywords: Coordination polymer; Crystal structure; Magnetic property;

Formation and magnetic property of an octanuclear metallamacrocycle-based three-dimensional metal organic framework by Zhouqing Xu; Huijun Li; Angran Li; Wei Meng; Hongwei Hou; Yaoting Fan (126-129).
In this article, a chiral azolate-based octanuclear metallamacrocycle three-dimensional (3D) complexes {[Co2(pbt)2(H2O)2] · 4.5H2O}n (1) have been synthesized and characterized. Complex 1 crystallizes in the space group P43212 and displays a complicate homochiral three-dimensional (3D) framework containing octanuclear cobalt metallamacrocycles. The trizole-N1, N2 bridging cobalt trinuclear secondary building units (SBUs) in complex 1 provides a platform to investigate the magneto-structural correlations. The weak magnetic exchange of this complex is due to the asymmetric doubly 1,2,4-triazole-N1,N2 bridged SBUs which reduces the ineffective overlap between the orbits of paramagnetic central ions.Octanuclear metallamacrocycle-based three-dimensional (3D) complex {[Co2(pbt)2(H2O)2] · 4.5H2O} n (1) containing unidirectional helixes has been synthesized and characterised. Magnetic susceptibility measurements reveal that this complex display antiferromagnetic coupling.Display Omitted
Keywords: Metal-organic framework; Octanuclear metallamacrocycle; Magnetic properties;

An array of enantiomerically pure mononuclcear [Ru(bpy)2(dppz)]2 + derivatives with 10,13-diaryl substituted dppz ligand has been synthesized and characterized (bpy = bipyridine, dppz = pyrido-[3,2-a:2′,3′-c]phenazine). These new complexes exhibit substantially similar absorption spectra, resembling the parent complex [Ru(bpy)2(dppz)]2 +, and the enantiomerically pure analogues show the similar CD spectra in buffer solution despite the structural difference.A series of enantiomerically pure mononuclcear [Ru(bpy)2(dppz)]2 + derivatives with 10,13-diaryl substituted dppz ligand has been synthesized and characterized.Display Omitted
Keywords: Ruthenium complexes; dppz; Enantiomer; 10,13-Diaryl;

Self-assembly of AgClO4 with bis(4-pyridyl)cyclotetramethylsilane (L) produces a 4-fold interpenetrating 3D coordination polymeric framework consisting of [Ag5(L)7(CH3CN)2](ClO4)5∙2CH3CN (1). The topological analysis indicates that the compound is the first example of a binodal 3,3-connected (82∙10)2-ete net topology. Its thermal behavior and photoluminescent properties have been investigated.Self-assembly of AgClO4 with bis(4-pyridyl)cyclotetramethylsilane (L) produces a 4-fold interpenetrating 3D coordination polymeric framework consisting of [Ag5(L)7(CH3CN)2](ClO4)5∙2CH3CN, which is the first example of a binodal 3,3-connected (82∙10)2-ete framework, according to topological analysis. Its thermal behavior and blue-light emitting properties have been investigated.Display Omitted
Keywords: Bis(4-pyridyl)cyclotetramethylsilane; Interpenetration; Photoluminescence; Silver(I); Topology;

Two new mixed-ligands Cu(II) complexes, [Cu(hfipbb)(2,2′-bipy)(H2O)2]n (1) and [Cu2(hfipbb)2-(4,4′-bipy)(H2O)]n (2) (H2hfipbb = 4,4′-(hexafluoroisopropylidene)bis(benzoic acid)), were prepared, which both show different 2D networks and the antiferromagnetic interactions between the adjacent Cu(II) ions as well as photocatalytic degradation activity for dye degradation.Two new mixed-ligands Cu(II) complexes [Cu(hfipbb)(2,2′-bipy)(H2O)2]n (1) and [Cu2(hfipbb)2(4,4′-bipy)(H2O)]n (2) present a two-dimensional (2D) supramolecular network and 2D undulating network, respectively. Notably, compounds 1 and 2 exhibit photocatalytic activity for degradation of rhodamine B (RhB) under visible-light.Display Omitted
Keywords: Cu(II) complexes; Mixed-ligands; Crystal structure; Magnetic property; Photocatalytic activity;

Two Keggin polyoxoanion-based hybrids composed of CuI/tbz segments: Syntheses, structures and electrochemical properties by Xiang Wang; Jun Peng; Kundawlet Alimaje; Zheyu Zhang; Zhenyu Shi (141-145).
Two Keggin polyoxoanion-based hybrid compounds composed of CuI/tbz segments [CuI 2(tbz)2][CuI(tbz)2(PMoVI 10Mo2 VO40CuI 2)] (1) and [CuI 2(tbz)3][CuI (tbz)2](PW12O40) (2), have been hydrothermally synthesized. In compound 1, a 3D supramolecular framework with 2D channels is constructed from a novel cap-to-cap {CuI(tbz)2(PMoVI 10Mo2 VO40CuI 2)}2 − n chain via hydrogen bonding and π–π interactions, in which {CuI 2(tbz)2}2 + segments are incorporated. Compound 2 is composed of one discrete PW12 polyoxoanion, one {CuI(tbz)2}+ segment and one {CuI 2(tbz)3}2 + segment, displaying a 3D supramolecular structure through hydrogen bonding and π–π interactions. The results indicate that the polyoxoanions and configurations of tbz ligand play the key roles in the self-assembly processes. The electrochemical properties of compounds 1 and 2 have been investigated.Two Keggin POM-based hybrids composed of CuI/tbz segments are synthesized. The polyoxoanions and configurations of tbz ligand play the key roles in forming structures.Display Omitted
Keywords: Polyoxometalates; CuI/tbz segments; Hydrothermal synthesis; Electrochemical property;

New lanthanide sulfate–oxalate hybrid solids containing different inorganic building blocks by Kangcai Wang; Yu Wang; Dingguo Xu; Daibing Luo; Zhien Lin (146-149).
Three new lanthanide sulfate–oxalate hybrid solids, Er2(SO4)(C2O4)2(H2O)6·0.5H2O (1), Nd3(SO4)(C2O4)3.5(H2O)7·H2O (2), and [C4H14N2]0.5·Nd2(SO4)2(C2O4)1.5(H2O)4 (3), have been synthesized and structurally characterized. Compound 1 has a rare ladder-like structure, while compounds 2 and 3 have different three-dimensional structures. The presence of large 12-ring channels in the structure of 3 is noteworthy. The powder X-ray diffraction, IR spectra, thermogravimetric analyses, and magnetic susceptibility measurements of compounds 1 and 2 have also been investigated.Three new lanthanide sulfate–oxalate hybrid solids have been synthesized and characterized. These compounds display different structures containing isolate ErO8 polyhedra, Nd2O16 dimers and inorganic chains of NdO9 polyhedra, respectively.Display Omitted
Keywords: Hydrothermal synthesis; Hybrid solid; Lanthanide; Sulfate; Oxalate;

A luminescent Cu(I)–CN-1,2,4-triazolate open-framework with unique 2-fold interpenetrated (4, 6)-connected fsc topology by Yan-Ting Feng; Shu-Ni Li; Quan-Guo Zhai; Yu-Cheng Jiang; Man-Cheng Hu (150-154).
Self-assembly of CuCN, K3Fe(CN)6 and 3,5-bis(4-pyridyl)-1,2,4-triazole (BPy-4Trz) ligand under hydrothermal conditions generated a novel hybrid crystalline compound, namely, {Cu2(BPy-4Trz)(CN)} n (1). Two kinds of binuclear motifs, [Cu2(Trz)2] and [Cu2CN], link each other through the 4-pyridyl and cyanide groups to give a three-dimensional (4,6)-connected open-framework of 1 with 2-fold interpenetrated fsc topology. The green fluorescence emissions are observed in the solid state at room temperature.Hydrothermal synthesis and photoluminescence of a unique Cu(I)–CN-1,2,4-triazolate open-framework with 2-fold interpenetrated (4, 6)-connected fsc topology.Display Omitted
Keywords: CuCN; 3,5-Bis(4-pyridyl)-1,2,4-triazole; Open-framework; Photoluminescence; Topology;

Three new Zn(II) coordination polymers with tetrazole-1-carboxylate ligand: Crystal structures and luminescent properties by Fang-Mei Jian; Shui-Dong Zhu; Shuang Jin; Zhong-Gao Zhou; Ying-Bing Lu (155-158).
Three novel Zn(II) complexes based on tetrazole-1-acetic ligand, Zn(1-tza)2(phen) (1), [Zn(1-tza)(2,2′-bipy)(H2O)]∙X (X = NO3 2, ClO4 3) (1-tza = tetrazole 1-acetic, phen = 1,10-phenanthroline, 2,2′-bipy = 2,2′-bipyridine), were synthesized and structurally characterized by single-crystal X-ray diffraction. Three different coordination modes of 1-tza ligand exist in the three obtained complexes. The 1-D chain of 1 is built by μ 2-1-tza bridges. Compounds 2 and 3 are isomorphous, and their structures show a 2-D (4,4)-connected net constructed from binuclear [Zn2(COO)2] unit and μ 3-1-tza linkers. Photoluminescence studies show that 1, 2 and 3 exhibit strong luminescence. The thermal analyses of the three complexes and the optical properties of 1 and 3 have also been investigated.The diversities of coordination modes of tetrazole-1-acetic (1-Htza) ligand lead to different structural networks of the three complexes: 1 with 1-D chained structure, 2 and 3 with 2-D (4,4)-connected framework. Photoluminescence studies show that the three complexes show strong luminescence, and the optical absorption spectra suggest complexes 1 and 3 possessing the wide gap semiconductor characters.Display Omitted
Keywords: Tetrazole 1-acetic; Crystal structure; Photoluminescence properties; Zinc(II);

A new self-assembled dinuclear rhenium(I) tricarbonyl complex, [Re2(CO)6(μ-η 4-C2O4)(μ-4,4′-tmdp)] (1) featuring a bis-chelating oxalato dianion (μ-η 4-C2O4, H2C2O4  = oxalic acid) connects two fac-Re(CO)3 cores, which are interconnected by a neutral ditopic N-donor clip ligand, that is, 4,4′-trimethylenedipyridine (μ-4,4′-tmdp) has been elegantly synthesized in high yield in a one-step reaction. Compound 1 was characterized by elemental analysis, IR, ESI-MS, TGA and single-crystal X-ray diffraction analyses. The titled complex represents the first dirhenium(I) metallacycle which shows the coexistence of two emissive pathways at room temperature, one populates an emissive 3π–π* state and the other populates a 3MLCT state.Presented here is a new self-assembled m-oxalato-bridged dirhenium(I) metallacycle, namely, [Re2(CO)6(m-h4-C2O4)(m-4,4¢-tmdp)] (1, H2C2O4  = oxalic acid, 4,4¢-tmdp = 4,4¢-trimethylenedipyridine), which features the coexistence of two emissive pathways from an emissive 3p−p* and a 3MLCT state at room temperature.Display Omitted
Keywords: Dual emission; Flexible ligand; Rhenium(I); Self-assembly; X-ray crystallography;

A novel three-dimensional (3-D) Dy(III)–Cu(I) heterometallic polymer, [Dy2(pca)2(npa)2(H2O)3](Cu2I2) (1, pca = 2-pyrazinecarboxylic acid, npa = 1,8- naphthalenedicarboxylic acid), has been synthesized by hydrothermal reactions of Dy2O3, CuI, 2-pyrazinecarboxylic acid, 1,8-naphthalene anhydride in water in the presence of HClO4. Compound 1 has been characterized by elemental analysis, infrared spectroscopy, powder X-ray diffraction and single-crystal X-ray diffraction analysis, respectively. The thermal stability and luminescence property of compound 1 have also been studied. Single crystal X-ray diffraction analysis reveals that compound 1 contains two distinct units of 1-D Dy–carboxyl belt and Cu–I chain. The two types of 1-D units are further linked via pca ligands to give a heterometallic Dy–Cu framework.A novel three-dimensional (3-D) Dy–Cu heterometallic polymer 1 contains two distinct units of 1-D Dy–carboxyl belt and Cu–I chain. The two types of 1-D units are further linked via pca ligands to give a heterometallic Dy–Cu framework. The two different types of 1-D building units are rarely observed in the reported heterometallic framework.Display Omitted
Keywords: Hydrothermal; Heterometallic; Copper(I)–dysprosium(III); Dual ligand;

A novel POM-based inorganic porous framework: Synthesis, structure and properties by Yingying Sun; Jing Lu; Dacheng Li; Jianmin Dou (166-169).
A novel POM-based inorganic porous framework, (H2en)3[Mn3P4Mo4O28] 1 (en = ethylenediamine),has been hydrothermally synthesized and characterized by elemental analyses, IR spectroscopy, TG analyses, and single crystal X-ray diffraction. In compound 1, PO4 groups link Mn atoms to form three-fold interpenetrated adamantane networks; the Mo-O helical chains connect with the adamantane networks through μ2-bridging oxygen atoms and PO4 groups. The PO4, MnO4, MnO6 and MoO6 polyhedrons share corners and connect with each other to form a 3-D complicated framework with 1-D channels. And the channels are filled with the diprotonated ethylenediamine cations. The magnetic behavior of 1 is antiferromagnetic coupling. Futhermore, compound 1 exhibits good thermal stability and active electrochemical behavior.In compound 1, PO4 groups link Mn atoms to form three-fold interpenetrated adamantane networks, which are further linked by the Mo-O helical chains through μ2-bridging oxygen atoms and PO4 groups. The PO4, MnO4, MnO6 and MoO6 polyhedrons share corners and connect with each other to form a 3-D complicated framework with 1-D channels filled by diprotonated ethylenediamine cations. This POM-based inorganic porous framework shows remarkable stability and excellent electrocatalytic activity.Display Omitted
Keywords: Multifunctional porous material; Adamantane network; Helical chain;

The well-soluble tetrathiafulvalene carboxylic derivative [Bu4N]2[TTF(COOH)2(COO)2] (L) has been used to create the interesting 3D supramolecular network [Mn(H2O)4(CH3OH)2][TTF(COOH)2(COO)2] (1), driven by O–H⋅⋅⋅O interaction. The absorption spectra and electrochemical behavior of L and 1 have been discussed. Optimized conformation and molecular orbital diagram of L have been calculated with density functional theory.A well-soluble TTF–carboxylic derivative L has been synthesized. By ion exchange reaction, an interesting 3D supramolecular network 1 was obtained. Their electrochemical and absorption behaviors have been measured and analyzed. The results suggest that the TTF–carboxylic ligand is useful for building intriguing supramolecular systems.Display Omitted
Keywords: Tetrathiafulvalene; Carboxylic ligand; Hydron-bonding; Redox chemistry;

A new 3D coordination polymer, Mn2(atz)(isonic)(OH)(Cl)]n (1), was synthesized hydrothermally from mixed-ligands of Hatz (Hatz = 5-amino-tetrazolate) and Hisonic (Hisonic = isonicotinate) and corresponding metal salts. It was characterized by IR spectra, elemental and thermal analysis, single crystal and powder X-ray diffraction. Variable temperature magnetic investigations indicate that compound 1 exhibits typical antiferromagnetic behaviors.A new coordination polymer, Mn2(atz)(isonic)(OH)(Cl)]n has been firstly synthesized by employing mixed-ligand synthetic approach. Compound 1 presents a 3D framework with an unprecedented (3,6,6)-connected topological network.Display Omitted
Keywords: Coordination polymers; Topological network; Mixed-ligand; Tetrazole; Magnetic properties;

Two new complexes {[Cd(bmimx)0.5(tbip)(H2O)] · H2O}n (1) and [Zn(bmimx)(tbip)]n (2) (bmimx = 1,4-bis(2-methylimidazol-1-ylmethyl)-2,3,5,6-tetramethylbenzene, H2tbip = 5-tert-butyl isophthalic acid) based on mixed ligands have been hydrothermally synthesized by varying the metal ions. Structural analysis reveals that complex 1 displays a 2D layer structure with a 44-sql topology; complex 2 exhibits a 3D 4-fold interpenetrated framework with sra topology. The structural differences between 1 and 2 indicate that metal ions have significant effects on the formation of the final architectures. In addition, the thermal stabilities and photoluminescent properties of the two complexes were also investigated.Two new complexes were prepared from reactions of bmimx and H2tbip with different metal salts. Structural determinations show that the structure spans from 2D layer to 3D 4-fold interpenetrated framework, which indicates that metal ions play an essential role in the formation of the architectures.Display Omitted
Keywords: Cadmium coordination polymer; Zinc coordination polymer; 1,4-Bis(2-methylimidazol-1-ylmethyl)-2,3,5,6-tetramethylbenzene; 5-Tert-butyl isophthalic acid; Crystal structures;

The synthesis, characterization by X-ray crystallography, photophysical properties and DFT calculations of bis(2-quinolyl)phenyl iridium complexes are reported here. The quinolyl-substituted iridium(III) compounds, which have amidate ancillary ligand, formed four-membered ring structure and have been employed for polymerization reaction and gave the metal-containing amide homopolymers.The synthesis, characterization by X-ray crystallography, photophysical properties and DFT calculations of bis(2-quinolyl)phenyl iridium complexes are reported here. The quinolyl-substituted iridium(III) compounds, which have amidate ancillary ligand, formed four-membered ring structure and have been employed for polymerization reaction and gave the metal-containing amide homopolymers. Display Omitted
Keywords: Iridium; Quinoline; Amidate ancillary ligand; Organometallic polymers; Four-membered ring;

A new 3D lanthanide metal–organic framework Eu(BPT)(DMF)(H2O)•(H2O)0.5] (1) has been synthesized by self-assembly of Eu(III) ions and ligand biphenyl-3, 4′, 5-tricarboxylate under solvothermal reaction conditions. X-ray crystallography reveals that 1 exhibits a (3, 6)-connected topology, with dinuclear europium clusters as 6-connected nodes and C2-symmetric ligands BPT as 3-connected nodes. In addition, the luminescence sensitization of 1 via excitation of the ligand is highly efficient.A new 3D europium MOF, Eu(BPT)(DMF)(H2O)•(H2O)0.5] (1)) has been synthesized by self-assembly of Eu(III) ions and ligand biphenyl-3, 4′, 5-tricarboxylate under solvothermal reactions. X-ray crystallography reveals that 1 exhibits a (3,6)-connected topology. In addition, the luminescent property of the compound was investigated.Display Omitted
Keywords: Metal–organic framework; Biphenyl-3,4′,5-tricarboxylic acid(H3BPT); Europium; Structural analysis; Luminescence;

One new title compound [Co(BIBP)(mpa)] n (1) (BIBP = 4,4′-biimidazole biphenyl, mpa = m-phthalic acid) has been synthesized under solvothermal condition. The title compound was characterized by IR spectra, thermal analysis, single crystal and powder X-ray diffraction. The results prove that the alliance of BIBP and aromatic carboxylic acids is good for diversity of the getatable structure. Magnetic susceptibility measurements indicate that compound 1 exhibits antiferromagnetic coupling between adjacent Co(II) ions. In addition, the photochemical properties have been investigated.One new title compound [Co(BIBP)(mpa)] n has been synthesized under solvothermal condition. Magnetic susceptibility measurements indicate that compound exhibits antiferromagnetic coupling between adjacent Co(II) ions.Display Omitted
Keywords: Co coordination polymer; Crystal structure; Magnetic property;

Two new three-dimensional metal–organic frameworks, [H2N(CH3)2]2[Zn(btec)]·DMF (1, H4btec = 1,2,4,5-benzenetetracarboxylate acid) and [H2N(CH3)2][ZnLi(btec)]·DMF (2), have been solvothermally synthesized and structurally characterized by single crystal X-ray diffraction. Compound 1 based on μ4-btec features an anionic homometallic framework with 4-connected pts topology. Compound 2 is a heterometallic organic framework with rare (4, 4, 8)-connected network topology, which can be considered as constitute of a Li-btec (pts) net and a Zn-btec net. Moreover, the luminescent properties of two compounds are investigated in the solid state at room temperature.Two new 3D homometallic and heterometallic metal–organic frameworks were synthesized and structurally characterized as a pts network and a rare (4, 4, 8)-connected network.Display Omitted
Keywords: MOFs; Zinc; Lithium; Topology; Photoluminescence; Crystal structure;

o-Hydroxybenzoyl hydrazine and p-hydroxybenzoyl hydrazine react with 1,3-dimethyl-5-acetyl-barbituric acid in ethanol to give H2L1 (85% yield) and H2L2 (91% yield) respectively. The copper(II) complexes with DMSO adducts, [Cu(L1)(DMSO)] and [Cu(L2)(DMSO)], were prepared by the stoichiometric reaction of the CuCl2·5H2O with the H2L1 and H2L2 in a molar ratio (M:L) of 1:1 in DMSO/water mixture. All compounds have been fully characterized using conventional spectroscopic techniques. X-ray structure analysis was carried out on the [Cu(L1)(DMSO)] which crystallizes in the triclinic P-1 space group. In addition, both ligands were applied several antioxidant assays including total antioxidant activity by phosphomolybdate, ferric reducing antioxidant power (FRAP) and scavenging activity on 1,1-diphenyl-2-picrylhydrazyl (DPPH). The results from antioxidant assays have shown that both ligands have excellent activities. o-Hydroxybenzoyl and p-hydroxybenzoyl hydrazone derivatives of 1,3-dimethyl-5-acetyl-barbituric acid as well as their copper(II) complexes with DMSO adducts were synthesized. X-ray structure analysis was carried out on the [Cu(L1)(DMSO)] which crystallizes in the triclinic P-1 space group. In addition, both ligands were applied three antioxidant assays. The results from antioxidant assays have shown that both ligands have excellent activities.Display Omitted
Keywords: Hydrazone; Copper(II) complexes; Barbituric acid; Free radical scavenging; FRAP;

The reactions of H4L1 (L1  =  N 1,N 1,N 2,N 2-tetra((2-hydroxy-3,5-dibutyl)benzyl)-1, 2-ethanediamine) and H4L2 (L2  =  N 1,N 1,N 2,N 2-tetra((2-hydroxy-3,5-dimethyl)benzyl)-1,2-ethanediamine) with AlMe3 in toluene give [Al2(CH3)2L1(THF)2] (1) and[Al2(CH3)2L2] (3) respectively. Treatment of complex 1 with 2-methoxyethanol affords [Al2(OCH2CH2OCH3)2  L1] (2). The experimental results indicate that complexes 1 and 2 can efficiently initiate the ring-opening polymerization of ε-caprolactone under a controlled manner, yielding polymers with relatively narrow molecular weight distribution and desirable molecular weights, while the performance of dinuclear complex 3 is not good due to the side reactions between the two neighboring active groups in the propagation progress.The reaction of H4L1 (L1  =  N 1,N 1,N 2,N 2-tetra((2-hydroxy-3,5-dibutyl)benzyl)-1,2-ethanediamine) with AlMe3 in toluene give [Al2(CH3)2L1(THF)2] (1). The experimental results indicate that complexes 1 efficiently initiate the ring-opening polymerization of ε-Caprolactone under a controlled manner, yielding polymers with relatively narrow molecular weight distribution and desirable molecular weights.Display Omitted
Keywords: Aluminum complex; ε-Caprolactone; Initiator; Ring-opening polymerization;

Quantitative estimation of the antiferromagnetic interaction between Cu(II) and Sm(III) in two dimensional heterometallic coordination polymer with isonicotinic acid as tectons by Sandip Saha; Debabrata Biswas; Partha Pratim Chakrabarty; Dieter Schollmeyer; Atish Dipankar Jana; Hiroshi Sakiyama; Masahiro Mikuriya (212-215).
The syntheses, structure and magnetic property of a novel two dimensional 3d–4f coordination polymer 2 [CuSmL(NO3)2(IN)], 1 (L2−   =  N, N′- propylenedi (3-ehoxysalicylideneiminato), the dianion of the Schiff base obtained from the 2:1 condensation of 3-ethoxysalicylaldehyde with 1,3-propanediamine, IN  = the isonicotinate ion) has been reported. The heterobinuclear units are connected through exo-bidentate ligands IN, leading to an extended 2D structure. A fit of the magnetic susceptibility data yields g Cu  = 2.109, g Sm  = 0.476, J CuSm  = − 0.893 cm− 1, θ  = − 3.37 K, and TIP = 0.001257 emu K mol− 1 with a good discrepancy factor of R χ  = 4.4 × 10− 5. This is the first quantitative estimation of the strength of the antiferromagnetic interaction between Cu(II) and Sm(III) ions to the best of our knowledge.The syntheses, structure and magnetic property of a novel two dimensional 3d–4f coordination polymer 2 [CuSmL(NO3)2(IN)] has been reported here. Structurally, this compound is the Cu–Sm containing 3d–4f two dimensional polymer connected by isonicotinate ion. From the magnetic view-point, any group have not reported on the variable temperature magnetic study of these particular types of two dimensional 3d–4f coordination polymers containing isonicotinate ion to the best of our knowledge. It is also notable that the magnetic interaction between CuII–SmIII ions is antiferromagnetic which were predicted in a qualitative and semi quantitative manner in earlier all cases, but for the first time we have reached to the estimated strength of antiferromagnetic interaction between these two ions.Display Omitted
Keywords: Heterometallic; Coordination polymer; Two dimensional; Antiferromagnetic interaction;

Synthesis and structure of Pb13Na(μ3-O)(μ3-OH)(BDC)12: A holodirected/hemidirected mixed Pb–Na heterometal coordination polymer with Pb12O20 cage by Jing Shi; Xiao-lin Liu; Yun Yan; Yun-feng Dong; Jie Li; Feng Wang; Xiu-jie Gu; Yan Jiang; Dong-hai Xu; Huan Chen (216-219).
By using the 1,3-benzenedicarboxylates (1,3-BDC) ligand in the hydrothermal reaction with Pb(NO3)2, we obtained a novel coordination polymer Pb13Na(μ3-O)(μ3-OH)(BDC)12. The Pb atoms and the 1,3-BDC ligands connect to each other and form a 3-D infinite framework which contains a Pb12 icosahedron and an O20 dodecahedron. These two polyhedrons construct a novel Pb12O20 large cage. The high-coordinated Pb atoms in Pb12 cluster have abnormal hemidirected coordination geometries because of the rigidity of the cluster, while the other eight-coordinated Pb atoms have holodirected geometry. Pb13Na(μ3-O)(μ3-OH)(BDC)12 has a similar structure with the M@Pb12 Zintl ion.The Pb atoms and the 1,3-BDC ligands connect to each other and form a 3-D infinite framework which contains a novel Pb12O20 large cage.Display Omitted
Keywords: Coordination geometry; Coordination modes; Crystal structure; Lead; Pb12O20 cage;

A 3D six-connected non-interpenetrated α-Po framework with an unique hexanuclear CuII cluster periodically extended by isophthalatlate (ip2 −) and N,N′-(1,1-methyl)-bis(imidazole) (mbim) ligands, [Cu3(μ 4-O)(mbim)(ip)2] n (1), has been hydrothermally synthesized and structurally characterized. The complex displays high thermal stability until 285 °C confirmed by thermal analysis and possesses a remarkable catalytic activity for degradation of congo red dye in Fenton process.A novel CuII coordination framework has been constructed by isophthalatlate (ip2 −) and N,N′-(1,1-methyl)-bis(imidazole) (mbim) mixed-ligands, which features a non-interpenetrated α-Po topology with unique hexanuclear CuII-oxo-clusters as nodes. The high catalytic property is also found in this complex.Display Omitted
Keywords: Catalytic property; Hexanuclear CuII cluster; Metal-cluster based coordination polymer;

Scalene-tricopper(II) bridged by 5-(1H-benzo[d]imidazol-2-yl-1H-imidazole-4-carboxylic acid: Synthesis, crystal structure and magnetic properties by Jia Shao; Qiang Ge; Yan Ouyang; Cheng-Zhi Xie; Xiao-Tong Zhang; Jing-Yuan Xu; Yves Journaux (224-226).
New scalene tricopper complex [CuII 3(HImbm)(bipy)6](ClO4)4  · 3CH3OH · 4H2O (1) (H3Imbm = 5-(1H-benzo[d]imidazol-2-yl)-1H-imidazole-4-carboxylic acid, bipy = 2,2′-bipyridine) was synthesized. X-ray analysis reveals that 1 crystallizes in monoclinic P2(1)/c. Complex 1 can be described as three terminal [Cu(bpy)2]2 + units bridged by one asymmetric H3Imbm ligand with its peripheral three chelating pockets to capture three Cu atoms in a scalene-triangular geometry. The variable-temperature magnetic measurement was recorded for the crystallographically characterized 1, and the magnetic response was analyzed very well using a scalene triangle Cu3 model, indicating a dominant antiferromagnetic coupling with J 12  = − 44.3 cm− 1, J 23  = − 27.3 cm− 1, and g  = 2.08, given J 13  = 0.New scalene tricopper complex [CuII 3(HImbm)(bipy)6](ClO4)4  · 3CH3OH · 4H2O (1) (H3Imbm = 5-(1H-benzo[d]imidazol-2-yl)-1H-imidazole-4-carboxylic acid, bipy = 2,2′-bipyridine) displayed a dominant antiferromagnetic coupling with J 12  = − 44.3 cm− 1, J 23  = − 27.3 cm− 1, and g  = 2.08, given J 13  = 0 with R  = 4.3 × 10− 6.Display Omitted
Keywords: Imidazole carboxylic bridge; Scalene-triangular copper; Magnetic property;

A Ni(II) coordination polymer namely {[Ni2(btc)2(bpy)2(μ-H2O)2(H2O)2][Ni(bpy)(H2O)4]}.4H2O (1) (H3btc is 1,3,5-benzenetricarboxylic acid and bpy is 2,2′-bipyridine) with nickel acetate tetrahydrate, was prepared under hydrothermal conditions and characterized by single crystal X-ray diffraction, FTIR, TGA and elemental analysis techniques. In compound (1), the asymmetric part of the unit cell was found to contain two independent halves of centrosymmetric, binuclear water-bridged complex [Ni2(μ-H2O)2(H2O)2(btc)2(bpy)2]2 −, an equivalent of the [Ni(bpy)(H2O)4]2 + complex and four uncoordinated water molecules. Single crystal X-ray analysis revealed that the complex crystallizes in the triclinic P-1 space group, with a = 9.0787(3) Å, b = 10.5726(4) Å, c = 30.0065(11) Å, α = 83.439(3)°, β = 88.213(3)° and γ = 65.361(4)°. A 3D coordination polymer network as a supramolecular structure is formed by means of numerous hydrogen bonds involving all hydrogen atoms from water molecules and carboxylate groups of btc ligands.Synthesis of a coordination polymer of Ni(II) with formula {[Ni2(btc)2(bpy)2(μ-H2O)2(H2O)2][Ni(bpy)(H2O)4]}.4H2O is presented.Display Omitted
Keywords: Nickel(II) complex; 1,3,5-Benzenetricaboxylic acid; 2,2′-Bipyridine; Coordination polymer;

Two novel nanosized bipyrazolate-bridged metallo-macrocycles with dipalladium(II,II) corners, {[(bpy)Pd]8L4}(NO3)8 and {[(bpy)Pd]6L3}(NO3)6 [L = 1, 4-di(3′,5′-dimethyl-1H-pyrazolyl-4yl)naphthalene] have been synthesized through a directed self-assembly approach that involves spontaneous deprotonation of the 1H-bipyrazolyl ligand in aqueous solution. These crown-shaped complexes with deep cavities potentially served as the host to solvent molecules and anions. Such metallo-macrocyclic structures have been characterized by single-crystal X-ray diffraction analysis, elemental analysis, 1H and 13CNMR, high resolution electrospray ionization mass spectrometry, UV–visible spectroscopy, and luminescence spectroscopy.Two novel metallomacrocycles Pd8 and Pd6 coexisted in the same reaction, which self-assembled from bipz ligands and diPd coordination motifs. We selectively separated two supramolecular species by changing the recrystallization conditions in one-pot reaction.Display Omitted
Keywords: Metallo-macrocycle; Bipyrazolate ligands; Self-assembly; Luminescent;

2D pillar-chained lanthanide(III)-copper(I) metal–organic frameworks based on isonicotinate and in situ generated oxalate by Hong-Guang Jin; Ming-Fang Wang; Xu-Jia Hong; Jian Yang; Teng Li; Yan-Jun Ou; Ling-Zhi Zhao; Yue-Peng Cai (236-240).
Three isostructural lanthanide complexes, [Ln2(H2O)4(DMSO)](CuI)4(Ina)4(ox)[HIna = isonicotinic acid; H2ox = oxalic acid; Ln = Pr(1), Sm(2), Eu(3)], have been synthesized under the solvothermal condition and characterized by single-crystal X-ray diffraction, X-ray powder diffraction (PXRD), thermogravimetric analysis (TGA) and elemental analysis (EA) and IR spectra. Complexes 13 present 2-D pillar-chained frameworks and consist of two distinct chain-like motifs of inorganic [Cu4I4]n cluster chains and organic Ln-carboxyl-oxalic [Ln2(μ 2-Ina)2(Ina)2(μ 2-ox)]n chains. The 13C NMR of HIna indicates ox2 − in 13 is generated by the in situ decomposition of HIna. Additionally, the photoluminescent properties of 1–3 are also discussed.Three isostructural 2-D 3d–4f compounds have been successfully synthesized based on isonicotinate and in situ generated oxalate. The structures contain inorganic I–Cu clusters and organic Ln-carboxyl-oxalic chains bridged by isonicotinate linkers.Display Omitted
Keywords: 3d–4f pillar-chained MOFs; In situ reaction; Fluorescence;

In this paper, Zn3(BTC)2 (BTC: 1,3,5-benzenetricarboxylate) films were successfully fabricated on the substrate of a zinc plate using in situ microwave. The structure and morphology of the obtained MOF films were characterized by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), and so on. And the Zn3(BTC)2 film shows a better performance in the photodegradation of MB dye than the commercial TiO2 powder under the similar conditions. The experimental results also confirmed that the Zn3(BTC)2 film displays well long-term stability.The Zn3(BTC)2 film was fabricated on the substrate of a zinc plate using in situ microwave irradiation, and the Zn3(BTC)2 film shows a better performance in the photodegradation of MB dye than the commercial TiO2 powder under similar conditions.Display Omitted
Keywords: Metal–organic frameworks; Microwave; Film; Photocatalytic;

Synthesis and electro-catalytic properties of a dinuclear triazenido-palladium complex by Jing Chu; Qi-ying Lv; Jie-ping Cao; Xiao-hua Xie; Shuzhong Zhan (245-248).
The reaction of 1,3-bis[(4-chloro)benzene]triazene (HL) and [Pd(CH3CN)4]Cl2 gave a dinuclear triazenido complex Pd2L4 1, which has been characterized by 1H NMR spectrum and X-ray crystallography. Electrochemical studies showed that complex 1 is capable of generating hydrogen from acetic acid in DMF with icat /ip  ~ 7.5.The reaction of 1,3-bis[(4-chloro)benzene]triazene (HL) and [Pd(CH3CN)4]Cl2 gave a dinuclear palladium(II) complex Pd2L4 1, which can generate hydrogen from acetic acid in DMF with icat /ip  ~ 7.5.Display Omitted
Keywords: Triazenido-palladium complex; Crystal structure; Molecular electro-catalyst; Hydrogen evolution;

Presented in this communication are four metal complexes based on 2-propyl-4,5-dicarboxylate-imidazole (H3PIDC), including two Co(II) coordination compounds, [Co(H2PIDC)2(H2O)2] · 4H2O (1) and 2[Co(H2PIDC)2(H2O)2] · 5H2O (2), as well as two Zn(II) coordination compounds, [Zn(H2PIDC)2(H2O)2] · 4H2O (3) and 2[Zn(H2PIDC)2(H2O)2] · 7H2O (4). They contain the same coordinated unit of [M(H2PIDC)2(H2O)2] (M = Zn or Co). Interestingly, among these four complexes, 1 and 2, or 3 and 4 crystallized in different space group, which may be related with the number of the crystallized H2O molecules.Presented in this communication are four metal complexes based on 2-propyl-4,5-dicarboxylate-imidazole (H3PIDC). They contain the same coordinated unit. Interestingly, due to different numbers of the crystallized H2O molecules within them, they show different crystallized states. The lattice H2O molecules induced diverse crystallized states is quite novel and interesting.Display Omitted
Keywords: Zinc; Cobalt; 2-Propyl-4,5-dicarboxylate-imidazole (H3PIDC);