Inorganic Chemistry Communications (v.13, #11)

Contents List (iii-xii).

A en-templated 3D coordination polymer based on H2pzdc with macrometallocycles by Hai-Ning Wang; Jun-Sheng Qin; Dong-Ying Du; Guang-Juan Xu; Xin-Long Wang; Kui-Zhan Shao; Gang Yuan; Lian-Jie Li; Zhong-Min Su (1227-1230).
A new Zn(II) coordination polymer, [Zn3(pzdc)4]·en (1) (H2pzdc = pyrazine-2,3-dicarboxylic acid, en = ethylenediamine), has been prepared under hydrothermal condition. X-ray diffraction analysis shows that 1 has a 3D structure with micropores (calcd. 4.074 × 6.444 Å2) along the [1 0 0] direction filled with en guest molecules. Notably, the pzdc groups connect Zn(II) cations to form a macrometallocycle as the subunit, which is further connected to generate the final framework. Additionally, the luminescent property of compound 1 has been investigated in detail.A new Zn(II) coordination polymer (1), has been prepared. Compound 1 has a 3D structure with micropores along the [1 0 0] direction filled with en guest molecules. Notably, the pzdc groups connect Zn(II) cations to form a macrometallocycle as the subunit further connected to generate the final framework.Display Omitted
Keywords: Coordination polymer; Zinc(II); Template; Macrometallocycle; Luminescence;

A new multifunctional linkage Calix-AC-Si is derived from the modification of the p-tert-butylcalix[4]arene derivative with 3-(triethoxysilyl)-propyl isocyanate (TEPIC) and behaves as the first chelated ligand, and the organic polymer polyvinylpyridine (PVPD) is used as the second terminal ligand, whose ternary hybrids of metal ions (Tb3+ and Zn2+) are assembled and possess different luminescent properties. Especially the introduction of Zn2+ in the Tb3+ hybrid system can improve the luminescence of Tb3+.Ternary metal ion (Tb3+ and Zn2+) hybrids with new multifunctional linkage Calix-AC-Si and the organic polymer polyvinylpyridine (PVPD) have been assembled and possess different luminescent properties.Display Omitted
Keywords: Ternary inorganic/organic hybrids; Coordination bonding assembly; p-tert-Butylcalix[4]arene derivative; Polyvinylpyridine; Photoluminescence;

The reaction of 1 equivalent of pyrazine (pyz) with two equivalents of Ln(fod)3 units led to isolation of first example of pyrazine-bridged dinuclear lanthanide β-diketonate complexes of the form [Ln(fod)3(μ-pyz)Ln(fod)3] (where fod is the anion of 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione and Ln = La, Pr, Nd and Sm). Amazingly only early lanthanides form pyrazine-bridged dinuclear Ln(fod)3 complexes, although the entire series was explored. The high yield, elemental analysis and NMR of the isolated complexes strongly support their dinuclear nature. The solution structure of the complexes was investigated by 1H NMR and 4f4f absorption spectroscopy which confirm their dinuclear nature. The luminescence of Sm–Sm complex, in solution, has been investigated and discussed.The reaction of 1 equivalent of pyrazine (pyz) with two equivalents of Ln(fod)3 units (fod is the anion of 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione) led to the isolation of first examples of pyrazine-bridged dinuclear lanthanide (Ln = La, Pr, Nd and Sm) β-diketonate complexes of the form [Ln(fod)3(μ-pyz)Ln(fod)3].Display Omitted
Keywords: Lanthanide complexes; Pyrazine-bridged complexes; NMR; 4f–4f absorption; Lanthanide luminescence;

Two coordination polymers [Zn2(H2L)2(bbi)(H2O)2·H2O] n 1 and [Ni4(L)2(bbi)2(H2O)4·H2O] n 2 {H4L = methylenediisophthalic acid, bbi = 1,1′-(1,4-butanediyl)bis(imidazole)} have been prepared under hydrothermal conditions and structurally characterized by X-ray diffraction analyses. Mononuclear 1 is a 1D ladder chain and bbi adopts trans-configuration linking two metal centers. Plus the hydrogen binding interactions, it formed a 3D two-fold perpendicular interpenetrating (4, 5)-connected framework. Binuclear units of 2 are connected by L4− and cis-bbi to generate a 3D (4, 6)-connected framework, in which twisted bbi with binuclear units generate the rare triflexure helix. In solid state, complex 1 exhibits yellowgreen emissions at ambient temperature. Magnetic measurements show that there exist weak ferromagnetic interactions in 2.Two coordination polymers, mononuclear 1 is 1D ladder chain, considering hydrogen bonds to form 2-fold interpenetrating (3, 4)-connected supramolecular architecture. Complex 2 is a 3D (4, 6)-connected network, in which binuclear units with bbi form rare triflexure helix.Display Omitted

One-dimensional coordination polymer {[1H,9H-ade]2[MnL2]∙4H2O} n (1) and {[1H,3H-cyt]2[CuL2]∙6H2O} n (2) (ade = adenine, cyt = cytosine, L = dianion of 2,3-pyridinedicarboxylic acid) are selectively synthesized and variable-temperature magnetic susceptibility measurements revealed weak antiferromagnetic interactions within the chains of 1 and 2 (J  = − 0.29 cm− 1 for 1 and J  = −0.03 cm− 1 for 2, according to the − 2J ij S i S j HDvV Hamiltonian formalism).One-dimensional coordination polymer {[1H, 9H-ade]2[MnL2]∙4H2O}n and {[1H,3H-cyt]2[CuL2]∙6H2O}n (ade = adenine, cyt = cytosine, L2- = dianion of 2,3-pyridinedicarboxylic acid) are selectively synthesized and variable-temperature magnetic susceptibility measurements revealed weak antiferromagnetic interactions within the chains of the coordination polymers.Display Omitted
Keywords: Coordination polymer; 2,3-Pyridinedicarboxylic acid; Copper(II); Manganese(II); Nucleobase; Magnetochemistry;

Four novel Cr(III) complexes, Bis(ethylenediamine-κ 2N,N′)(R-SA-κ 2O,O′)chromium(III) chloride (H2SA = salicylic acid, R = 5-F, 5-Cl, 5-Br, 4-CH3 ethylenediamine = en) have been synthesized and three of them are determined by X-ray crystallography. The competition reaction with EDTA and apoovotransferrin (apoOTf) was monitored by UV–Visible (UV–vis) and fluorescence spectra at 37 °C. The reaction with EDTA is only a simple competitive process and no specific selectivity was observed (k EDTA/F410  = 4.07 × 10−3–4.37 × 10−3  M−1  s− 1). While for the reaction with apoOTf, an instable intermediate species (R-SA)–Cr(III)–OTf forms (k OTf/F336  = 1.70 × 10− 1–2.08 × 10−1  M−1  s− 1), where R-SA2− act as the role of synergistic anion. The intermediate is instable and the R-SA2− ligand will then be released with the rate constants of 1.17 × 10− 1 (5-F-SA2−) ≈ 1.01 × 10− 1 (4-CH3-SA2−) > 3.19 × 10− 2 (5-Cl-SA2−) > 3.25 × 10− 3 (5-Br-SA2−) M−1  s− 1. The substitutive groups R on SA have positive influence on charge density of O donor atom, which directly affect the stability of the (R-SA)–Cr(III)–OTf intermediate.The substitutive group R on SA (H2SA = salicylic acid) has positive influence on the charge density of phenolate O and carboxylate O atom, which directly affect the stability of the R-SA–Cr(III)–OTf intermediate formed in the reaction of chromium complexes [Cr(III)(R-SA)(en)2]Cl with apoovotransferrin (OTf).Display Omitted
Keywords: Chromium(III); Salicylate derivate; Apoovotransferrin; EDTA;

Synthesis of four nine-coordinate lanthanide (III) complexes of the type, [Ln(hfaa)3(tptz)], where Ln = La, Nd, Sm and Tb; hfaa = the anion of 1,1,1,5,5,5-hexafluoro-2,4-pentanedione and tptz = 2,4,6-tris(2-pyridyl)-1,3,5-triazine, by a new modified one pot in situ method is reported. The lanthanide ions are coordinated to three N-atoms of three 2-pyridyl units of tptz besides six O-atoms of three hfaa units. The formation of these volatile complexes is confirmed by molecular ion peak in ESI-MS, IR and NMR. The hypersensitive 4G5/2, 2G7/2  ←  4I9/2 transition displays distinct band shape which is different from the band shape of known eight- and ten-coordinate complexes. The samarium and terbium complexes emit pink and green luminescence due to 4G5/2  →  6Hj (j = 5/2, 7/2, 9/2) and 5D4  →  7F j (j = 3-6) transitions, respectively.Synthesis of four nine-coordinate lanthanide (III) complexes of the type, [Ln(hfaa)3(tptz)] by a new modified one pot in situ method is reported. The samarium and terbium complexes are highly luminescent and emit pink and green luminescence, respectively.Display Omitted
Keywords: Lanthanide; 2,4,6-tris(2-pyridyl)-1,3,5-triazine; NMR; 4f–4f absorption; Luminescence;

A 3D pillared-layer porous framework, {[Co2(H2O)(μ 3-OH)(ptz)(nip)]·2H2O}n (1) (ptz = 5-(4-pyridyl)tetrazolate, nip = 5-nitroisophthalate), was in situ hydrothermally synthesized and structurally and magnetically characterized. Interestingly, the layered substructure of 1 consists of scarcely observed corner-sharing Co2(μ 3-OH) -chain and unprecedented pentadentate ptz ligand. More importantly, due to the mixed triple syn,syn-carboxylate-μ 3-OH-μ 4-tetrazolyl bridges as well as the triangular CoII arrangement, 1 behaves as a typical antiferromagnetically coupled paramagnet with a slight spin frustration, which exhibits a low-dimensional antiferromagnetic ordering below 10 K (Neel Temperature).A 3D pillared-layer porous framework, {[Co2(H2O)(μ 3-OH)(ptz)(nip)]·2H2O}n (1) (ptz = 5-(4-pyridyl)tetrazolate, nip = 5-nitroisophthalate), was in situ hydrothermally synthesized and structurally and magnetically characterized. Interestingly, the layered substructure of 1 consists of scarcely observed corner-sharing Co2(μ 3-OH) -chain and unprecedented pentadentate ptz ligand. More importantly, due to the mixed triple syn,syn-carboxylate-μ 3-OH-μ 4-tetrazolyl bridges as well as the triangular CoII arrangement, 1 behaves as a typical antiferromagnetically coupled paramagnet with a slight spin frustration, which exhibits an low-dimensional antiferromagnetic ordering below 10 K (Neel Temperature).Display Omitted
Keywords: Cobalt(II); Pyridyl tetrazolate; Pillared-layer framework; ∆-Chain; Spin frustration;

A new reduced zincic molybdophosphate, (H2bpp)3[Zn3Mo12 VO24(OH)6(H2O)2(HPO4)6(PO4)2]·2H2O 1 (bpp = 1,3-bis(4-pyridyl)propane) has been hydrothermally synthesized and characterized by elemental analysis, IR, TG, and single-crystal X-ray diffraction. Compound 1 crystallizes in the tetragonal space group I 41/a c d with a = 31.8033(4) Å, b = 31.8033(4) Å, c = 34.5593(8) Å, V = 34955.0(10) Å3, and Z = 16 and exhibits a 4,6-connected 3-D framework with (32.84)(34.42.83.95.10) topology. The basic building blocks of [Zn(2)(Mo6P4)2] are linked through [Zn(3)O6] octahedra and [Zn(1)O4] tetrahedra to construct 1-D chains along four different directions. Such 1-D chains are further connected by [Zn(1)O4]2+ linkers to form a 3-D intricate framework with helical channels occupied by protonated bpp and water molecules. Additionally, the electrochemical property of the 1-CPE has been studied in detail.A reduced zincic molybdophosphate,(H2bpp)3[Zn3Mo12 VO24(OH)6(H2O)2(HPO4)6(PO4)2]·2H2O (bpp = 1, 3-bis(4-pyridyl)propane), is reported for the first time. The compound exhibits a 4,6-connected 3-D framework with a (32·84)(34·42·83·95·10) topology. In this compound, the basic building blocks of [Zn(2)(Mo6P4)2] are linked through [Zn(3)O6] octahedra and [Zn(2)O4] tetrahedra to form a 3-D intricate framework with helical channels occupied by protonated bpp and water molecules.Display Omitted
Keywords: Hydrothermal synthesis; Zincic molybdophosphate; Three-dimensional framework; Topology; Electrochemical property;

2-Thiophene N(4)-methylthiosemicarbazone (HL) and its Ag(I) complex of formula [Ag6(L)6⋅ 4DMF] 1 have been synthesized and characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction studies. The silver(I) complex 1 with a 1:1 metal–ligand molar ratio is an unusual hexanuclear cluster with 6 silver atoms in different environments: four silver atoms of them are considered to be 3-coordinate form, which are coordinated by two thiolate sulfur atoms and one imine nitrogen and the other two silver atoms are considered to be 4-coordinate form, which are coordinated by three thiolate sulfur atoms and one imine nitrogen, with four thiolate sulfur bridging two silver atoms and two thiolate sulfur bridging three silver atoms. Biological studies, carried out in vitro against bacteria, fungi and SMMC-7721 liver cancer cell line, respectively, have shown that the free ligand and the title complex show distinct difference in the biological property.2-Thiophone N(4)-methylthiosemicarbazone and its Ag(I) complex of formula [Ag6(L)6⋅ 4DMF] 1 were synthesized and fully characterized. The silver complex 1 is an unusual hexanuclear cluster with 6 silver atoms in different environments. Biological studies have shown that the free ligand and the title complex show distinct difference in the biological property.Display Omitted
Keywords: Thiosemicarbazone; Silver(I); Crystal structure; Cytotoxic activity;

Striking medium effects on the kinetics of decomposition of macrocyclic Cu2+ complexes: Additional considerations to be taken when designing Copper-64 radiopharmaceuticals by Manuel G. Basallote; Carmen E. Castillo; M. Angeles Máñez; Přemysl Lubal; Manuel Martínez; Carlos Rodríguez; Jakub Vaněk (1272-1274).
The kinetics of decomposition of a macrocyclic Cu2+ complex is strongly dependent on the anions in solution. In particular, chloride anions accelerate significantly the decomposition process, even out of the stopped-flow time scale. Given the different Cl concentrations in biological media, the possibility of changes in the decomposition kinetics must be considered when designing 64Cu radiopharmaceuticals.Decomposition of a macrocyclic Cu2+ complex is strongly dependent on the anions in solution, chlorides accelerate significantly the decomposition process.Display Omitted
Keywords: Decomposition of copper complexes; Kinetics; Electrolyte media; Copper-64 radiopharmaceuticals;

Synthesis, structure and characterization of (NH4)2[Cu2(H2O)4(NH3CH2COO)2(NH2CH2COO)2]H2V10O28·6H2O by Lenka Klištincová; Erik Rakovský; Peter Schwendt; Gustav Plesch; R. Gyepes (1275-1277).
The decavanadate with a novel glycine–glycinato complex of copper (II) in the cationic part, (NH4)2[Cu2(H2O)4(NH3CH2COO)2(NH2CH2COO)2]H2V10O28·6H2O (1), has been prepared and characterized by elemental analysis, infrared and EPR spectroscopies. The triplet X band EPR spectrum of powdered sample evidenced magnetic interaction between the Cu(II) atoms in the dimeric unit which is probably realized through the bridging water molecules in this part of the complex. A single crystal X-ray diffraction study revealed that the structure of 1 contains cationic copper complex with a rare Cu(H2O)2Cu double bridge. In this cation, a simultaneous bidentate N, O– and monodentate O– coordination of glycine to the same central atom was observed for the first time.The decavanadate with a novel glycine–glycinato complex of copper (II) in the cationic part, (NH4)2[Cu2(H2O)4(NH3CH2COO)2(NH2CH2COO)2]H2V10O28·6H2O, has been prepared. An X-ray structure analysis revealed that the structure contains cationic copper complex with a rare Cu(H2O)2Cu double bridge. In this cation, a simultaneous bidentate N, O– and monodentate O– coordination of glycine to the same central atom was observed for the first time.Display Omitted
Keywords: Decavanadate; Glycinato complex; Copper (II); X-ray structure; EPR;

Two novel coordination polymers [Zn2(tib)(chda)Cl2] (1) and [Zn(tib)I]I (2) have been prepared by reactions of 1,3,5-tris(1-imidazolyl)benzene (tib) and 1,2-cyclohexanedicarboxylic acid (H2chda) with corresponding Zn(II) salts, respectively. Complex 1 has a three-dimensional (3D) structure with rare gra (graphite) topology, while 2 is a typical two-dimensional (2D) (4·82) network. The results revealed that the counteranion plays a subtle and important role in the assembly procedure. Photoluminescent property of the complexes was investigated.Two novel coordination polymers [Zn2(tib)(chda)Cl2] (1) and [Zn(tib)I]I (2) [tib = 1,3,5-tris(1-imidazolyl)benzene, H2chda = 1,2-cyclohexanedicarboxylic acid] with rare gra (graphite) topological 3D framework and 2D (4·82) network have been synthesized and structurally characterized, respectively.Display Omitted
Keywords: Znic(II) coordination polymers; Counteranion-directed assembly; gra topology; Photoluminescence;

A novel two-dimensional (2D) polyoxovanadate compound KV3O8 has been synthesized and characterized crystallographically. The 2D anionic frameworks consist of distorted VO6 octahedrons and VO5 square pyramids, which are linked to one another via μ 1-oxo, μ 2-oxo and μ 3-oxo atoms. The energy band structure, density of states (DOS), dielectric constant, refractive index and chemical bonds have been investigated by density functional theory (DFT).Display Omitted
Keywords: Polyoxovanadate; Crystal structure; DFT; Potassium; DOS;

Synthesis, crystal structure and photoluminescence of a new Cd(II) coordination polymer with unusual geometry by Wen-Qian Geng; Xian-Lei Li; Jian-Hui Yin; Hong-Ping Zhou; Jie-Ying Wu; Yu-Peng Tian (1285-1288).
A new coordination polymer 1 [CdL2(NO3)2]n (L: 3, 6-di-(1, 2, 4-triazole-1-yl)-N-ethylcarbazole) has been synthesized by self-assembly reaction and characterized by elemental analysis and IR spectroscopy. The single-crystal X-ray diffraction shows that the [CdL2(NO3)2]n crystallizes in the monoclinic system and C2/m space group and the Cd(II) atom is four-coordinated. The coordination polyhedron can be described as a rectangle which is rather infrequent. The coordination bonds, hydrogen bonds and ππ interactions shaped the 3D network structure. A possible formation mechanism was discussed. The optical property was also studied.The [CdL2(NO3)2]n crystallizes in the monoclinic system and C2/m space group and the Cd(II) atom is four-coordinated. The coordination polyhedron can be described as a rectangle which is rather infrequent. The coordination bonds, hydrogen bonds and ππ interactions shaped the 3D network structure. The solid-state fluorescent property was investigated at room temperature. Display Omitted
Keywords: Crystal structure; Weak interaction; Rectangle geometry; Photoluminescence;

The oxidation of alcohols to carbonyls was investigated by an efficient catalyst system comprising of Fe(III)–Schiff base–triphenylphosphine complex. The complex chloroN-(2-mercaptophenyl)salicylideneiminebis(triphenylphosphine)iron(III) showed higher activity for oxidation of various alcohols under relatively mild conditions.Fe(III)-Schiff base complexes with triphenylphosphine were effective in the oxidation of primary and secondary alcohols in acetonitrile–periodic acid system.▪
Keywords: Fe(III) complexes; Schiff base; Triphenylphosphine; Oxidation of alcohol;

Synthesis, structure and superoxide dismutase activity of a novel tetranuclear copper(II) complex Na2[Cu4Na2(TACNTA)4(H2O)6]·(H2O)26 by Qing-Xiang Li; Qiao Li; Rong Chen; Xiang-Liang Yang; Jing-Yan Zhou; Hui-Bi Xu (1293-1295).
A novel tetranuclear copper(II) complex Na2[Cu4Na2(TACNTA)4(H2O)6]·(H2O)26, where TACNTA is 1,4,7-triazacyclononane-1,4,7-triacetate, was synthesized and characterized by X-ray crystallography. The result shows that each copper(II) ion is six-coordinated to three nitrogen atoms and three oxygen atoms of ligand TACNTA and adopts distorted octahedral coordination geometry. The superoxide (·O2 ) dismutation activity of the complex was also investigated by the riboflavin–methionine–nitro blue tetrazolium assay.A novel tetranuclear copper(II) complex was synthesized and characterized X-ray crystallography. The activity of SOD of the complex has been researched.Display Omitted
Keywords: Crystal structure; 1,4,7-triazacyclononane-1,4,7-triacetate; Tetranuclear copper(II) complex; Superoxide dismutase mimic;

Mineralizer effect on the synthesis of two types of one-dimensional chains silver-selenogermanate and selenostannate by Hua–Gang Yao; Ren–Chun Zhang; Shou–Hua Ji; Min Ji; Yong–Lin An; Gui–Ling Ning (1296-1298).
Two type of one-dimensional compounds, K2Ag2GeSe4(2) and K3AgSn3Se8(4), were synthesized with thiophenol as a mineralizer, whilst two oligomers, Cs4Ge2Se6 (1) and K4Sn3Se8(3), were obtained in absence of thiophenol. Compounds 1 and 3 contain dimeric [Ge2Se6]4− and trimeric [Sn3Se8]4− anions, respectively. Compound 2 contains isolated GeSe4 tetrahedra connected by linear-coordinated Ag+ ions to form an infinite anionic chains [Ag2GeSe4]2−. The building blocks [Sn3Se8]4− are linked by tetrahedral coordinated Ag+ ions to generate infinite chain [AgSn3Se8]3− of 4.Two type of one-dimensional compounds, K2Ag2GeSe4(2) and K3AgSn3Se8(4), have been synthesized solvothermally by using of thiophenol acting as a minerlizer. While two oligomers, Cs4Ge2Se6 (1) and K4Sn3Se8(3), were obtained in absence of thiophenol. Compounds 1 and 3 contain dimeric [Ge2Se6]4– and trimeric [Sn3Se8]4– anions, respectively. Compound 2 contains isolated GeSe4 tetrahedra connected by linear-coordinated Ag+ ions to form an infinite anionic chains [Ag2GeSe4]2–. The building blocks [Sn3Se8]4– are linked by tetrahedral coordinated Ag+ ions to generate infinite chain [AgSn3Se8]3– of 4. Display Omitted
Keywords: Solvothermal synthesis; Selenidogermanate; Selenidostannate; Mineralizer;

Two transition-lanthanide metal-organic coordination polymers, {[CoLn2(Himdc)2(SO4)2(H2O)4]·H2O}n [Ln = Yb (1), Ho (2)] (H3imdc = imidazole-4, 5-dicarboxylic acid), have been synthesized by the hydrothermal reactions of lanthanide oxides, CoSO4·7H2O, H3imdc and H2O. Single-crystal X-ray diffraction analysis reveals that the isostructural complexes 1 and 2 possess unusual 2D wave-like heterometallic layers with 1D (Ln2O2CoO2)n and [Ln2(SO4)2]n inorganic chains constructed by the assembly of 1D left-/right-handed helical L–Ln2Co–L (L = Himdc) chains and SO4 2− anions, while a 3D framework is formed via hydrogen-bonding interactions interlayer.Two 2D coordination polymers, {[CoLn2(Himdc)2(SO4)2(H2O)4]·H2O}n [Ln = Yb (1), Ho (2)] (H3imdc = imidazole-4,5-dicarboxylic acid), have been prepared under hydrothermal conditions. The two structures exhibit same unusual 2D wave-like heterometallic layers with 1D (Ln2O2CoO2)n and [Ln2(SO4)2]n inorganic chains constructed by the assembly of 1D left-/right-handed helical L–Ln2Co–L (L = Himdc) chains and SO4 2− anions, while a 3D framework is formed via hydrogen-bonding interactions interlayer.Display Omitted
Keywords: 3d-4f; Metal-organic framework; Helical chains; Imidazole-4; 5-dicarboxylate;

Four novel 3D coordination polymers, {[K3Cu2(H0.5pdtc)2 (H2O)6]·(H2O)2} n (1), {[trans-K2Mn3(pdtc)2 (H2O)11]·H2O} n (2), {[trans-K2Mn3(pdtc)2 (H2O)10]·H2O} n (3) and {[cis-K2Cu2Mn(pdtc)2 (H2O)10]·H2O} n (4), were synthesized by the self-assembly of potassium pyridine-2,3,5,6-tetracarboxylate (K4pdtc) with metal salts. All of them contain infinite 1D stepwise chain. Notably, 24 have 2D network structures depending on the trans- and cis- hexacoordinated Mn(II) acting as connecters between the chains. Then, they further assemble into 3D or twin-plane structures by K(I) ions. 4 is the first Cu/Mn/K heterotrimetallic complex with H4pdtc. The (H2O)6 clusters in 1 arranged stepwise along the complex chains owing to the host chains' template effect. The variable–temperature magnetic measurements reveal that weak antiferromagnetic interactions exist in complexes 1 and 4.Self-assembly of pyridine-2,3,5,6-tetracarboxylic acid(H4pdtc) with metal salts gave four 3D coordination polymers, {[K3Cu2(H0.5pdtc)2(H2O)6]·(H2O)2} n (1), {[trans-K2Mn3(pdtc)2 (H2O)11]·H2O} n (2), {[trans-K2Mn3(pdtc)2(H2O)10]·H2O} n (3), and {[cis-K2Cu2Mn(pdtc)2(H2O)10]·H2O} n (4). They all contain stepwise chains. 2-4 are connected into 2D layers through trans-/ cis-[Mn(H2O)4]2+ units. 4 is the first Cu/Mn/K heterotrimetallic complex with H4pdtc.Display Omitted
Keywords: Pyridine-2,3,5,6-tetracarboxylic acid; Heterometallic complex; Water clusters; Trans- and cis- structures;

A hexagonal C 3-symmetric (H2O)7 guest fits well into a C 3-symmetric terbium complex cavity by Ai-Hong Yang; Hong-Ling Gao; Jian-Zhong Cui (1309-1313).
A C 3-symmetric terbium complex {[Tb2(pztc)3]⋅6.5H2O} n (1) (pztc = pyrazine-2,3,5,6-tetracarboxylate), with hexagonal cavities, has been synthesized under hydrothermal conditions and characterized by X-ray single-crystal diffraction, elemental analysis, IR, TGA, PXRD and fluorescence measurements. The layer structure of the 2D complex is just like the structure of graphite. The most appealing structure is that a hexagonal C 3-symmetric (H2O)7 guest fits into the hexagonal C 3-symmetric terbium complex cavity very fitly. Furthermore, when the water clusters are driven off, the framework does not collapse and the luminescence intensity increases.A hexagonal C 3-symmetric terbium complex {[Tb2(pztc)3]⋅6.5H2O} n (1) (pztc = pyrazine-2,3,5,6-tetracarboxylate), with hexagonal cavities, has been synthesized under hydrothermal conditions. The layer structure of the infinite 2D complex is just like the structure of the graphite. The most appealing structure is that a hexagonal C 3-symmetric (H2O)7 guest fits into the hexagonal C 3-symmetric terbium complex cavity very fitly.Display Omitted
Keywords: C 3-symmetry; Terbium complex; (H2O)7 cluster; Host–guest; Fluorescence measurements;

A new coordination complex [Cu(4-L1)](NO3)2·2H2O (1) based on the functionalized cyclen mono-N (4-picolyl)cyclen (4-L1) has been prepared and characterized by X-ray diffraction. The structure of 1 can be described as a monodimensional coordination polymer in which the macrocycle ligand acts as bridging ligand. Examination of the inter-chain distances revealed the presence of hydrogen bonds between oxygen atoms of the nitrate anions and the hydrogen atoms of two secondary amines of the macrocycle ligands, affording isolated “double-chain” units. The overall structure of 1 consists of alternating succession of cationic layers of infinite “double-chain” units and anionic nitrate-water H-bonded layers.A new coordination complex [Cu(4-L1)](NO3)2.2H2O (1) based on the mono-N (4-picolyl)cyclen (4-L1) has been prepared and characterized by X-ray diffraction. The structure of 1 can be described as a monodimensional coordination polymer in which the macrocycle ligand acts as bridging ligand.Display Omitted
Keywords: Coordination polymer; Bridging ligand; Functionalized macrocycle ligand; Copper(II) complexes;

The paper presents a combined experimental and computational study of the tricarbonyl rhenium(I) complex incorporating 2,2′-bis(4,5-dimethylimidazole) (tmbiimH2). The complex has been studied by IR, UV–Vis spectroscopy and X-ray crystallography. The electronic structure of [Re(CO)3(tmbiimH2)Cl] has been calculated with the density functional theory (DFT) method, and the electronic spectrum of the complex was investigated at the TDDFT level employing B3LYP functional in combination with LANL2DZ.The paper presents a combined experimental and computational study of the tricarbonyl rhenium(I) complex incorporating 2,2′-bis(4,5-dimethylimidazole) (tmbiimH2). The compound has been identified by elemental analysis, IR, UV–Vis spectroscopy and X-ray crystallography. The electronic spectrum of the complex has been investigated at the TDDFT level employing B3LYP functional in combination with LANL2DZ.Display Omitted
Keywords: Rhenium(I) carbonyl complexes; 2,2′-bis(4,5-dimethylimidazole); X-ray structure; UV–Vis spectrum; DFT and TDDFT calculations;

Arene ruthenium(II) p-chloroacetophenone phenylthiosemicarbazone complex mediated transfer hydrogenation of ketones by Mathiyazhagan Ulaganatha Raja; Elangovan Sindhuja; Rengan Ramesh (1321-1324).
A series of cationic half-sandwich arene ruthenium(II) complexes of general formula [Ru(η6-p-cymene)Cl(L)]Cl have been synthesized from the reaction of [Ru(η6-p-cymene)Cl2]2 with thiosemicarbazone derivatives (L). Characterization of the complexes were accomplished by analytical and spectral (FT-IR, UV–Vis, 1H NMR) methods. Single crystal structure determination reveals the presence of a pseudooctahedral three-legged piano stool conformation. All the complexes exhibit a quasi-reversible one electron reduction in the range from −0.75 to −0.85 V. Further, the catalytic activity of the titled complex has been investigated in the transfer hydrogenation of ketones in the presence of isopropanol/NaOH.The η6-p-cymene ruthenium(II)phenylthiosemicarbazone complexes were synthesized and characterized. One of the complexes [Ru(η6-p-cymene)Cl(L2)]Cl efficiently catalyzes the transfer hydrogenation of various ketones up to 99% conversion.Display Omitted
Keywords: Synthesis; Ruthenium(II)-p-cymene; Phenylthiosemicarbazone ligands; Structural characterization; Transfer hydrogenation;

Design, synthesis and properties of a trinuclear copper(I) cluster with a triazenide ligand by Wen-jun Lei; Xing-wu Tan; Li-jun Han; Shu-zhong Zhan; Bai-tao Li (1325-1328).
The reaction of methyl anthranilate, sodium nitrite, and 2-aminobenzothiazole produces a new triazenide, namely, 1-[(2-carboxymethyl) benzene]-3-[benzothiazole]triazene (HL). In the presence of Et3N, the reaction of HL and CuCl in THF/methanol gives a trinuclear copper(I) cluster [Cu3L3] THF CH3OH (1 THF CH3OH), which has been characterized by X-ray crystallography, cyclic voltammogram and emission spectrum. CV of 1 reveals two reversible waves at –0.06 and 0.83 V, which correspond to two one-electron oxidation of Cu3 units ([Cu3]4+/[Cu3]3+) and ([Cu3]5+/[Cu3]4+), respectively. 1 appears photoluminescent (λ max  = 502 nm) at room temperature.In the presence of Et3N, the reaction of 1-[(2-carboxymethyl) benzene]-3-[benzothiazole]triazene (HL) and CuCl in THF/methanol gives a trinuclear copper(I) cluster [Cu3L3]×THF×CH3OH (1×THF×CH3OH). CV of 1 reveals two reversible waves at - 0.06 and 0.83 V, which can be ascribed to the redox coupling of ([Cu3]4+/[Cu3]3+) and ([Cu3]5+/[Cu3]4+), respectively. 1 appears photoluminescence (lmax = 502 nm) at room temperature.Display Omitted
Keywords: Trinuclear copper(I) cluster; Triazenido ligand; Crystal structures; Luminesence;

Palladium-catalyzed Mizoroki–Heck coupling reactions using sterically bulky phosphite ligand by Eunhye Jung; Kyungho Park; Jaewook Kim; Hee-Tae Jung; Il-Kwon Oh; Sunwoo Lee (1329-1331).
A new catalytic system based on palladium-phosphite for Mizoroki–Heck coupling reactions of aryl iodide and bromide is described. An air-stable phosphite ligand afforded the desired products with high yields in the palladium-catalyzed Mizoroki–Heck reactions. The coupling of aryl iodides was optimized with 0.5 mol% Pd(OAc)2, 1 mol% phosphite 2, and K2CO3 in DMF solvent. For the coupling of aryl bromides, 1 mol% Pd(OAc)2 and 5 mol% phosphite 2 were required with Na2CO3 as base. As a coupling partner alkene, n-butyl acrylate, t-butyl acrylate, styrene and N-t-butyl acrylamide all showed good yields.Phosphite 2 was employed as the ligand in the Mizoroki–Heck reaction, it showed good reactivities in the coupling of aryl iodide and bromides with alkene derivativesDisplay Omitted
Keywords: Mizoroki–Heck reactions; Phosphite; Palladium; Aryl halides; Alkenes; Coupling reactions;

Three new d10 coordination polymers based on 2-(2-pyridyl)benzimidazole ligand: Synthesis, structures and properties by Cheng-Jun Wang; Ke-Fen Yue; Wei-Hong Zhang; Jun-Cheng Jin; Xiao-Ying Huang; Yao-Yu Wang (1332-1336).
Three coordination polymers containing 2-(2-pyridyl)benzimidazole (PyHBIm) ligand, namely {[Zn3(PyBIm)3(PyHBIm)2(tma)(H2O)]•H2O}n (1), [Zn(PyHBIm)(oba)]n (2), [Cd(PyHBIm)(oba)]n (3), (tma = trimesate, oba = 4,4′-oxybis-(benzoate)), have been prepared through hydrothermal reaction. Compound 1 exhibits one-dimensional (1D) helical structure. However, compounds 2 and 3 display 1D meso -helical structure. These 1D structures are further assembled into three-dimensional (3D) networks through aromatic ππ stacking interactions and hydrogen bonding interactions. Moreover they all exhibit strong photoluminescence at room temperature and may be good candidates for potential luminescence materials.Three new coordination polymers containing 2-(2-pyridyl)benzimidazole (PyHBIm) ligand, namely {[Zn3(PyBIm)3(PyHBIm)2(tma)(H2O)]•H2O}n (1), [Zn(PyHBIm)(oba)]n (2), [Cd(PyHBIm)(oba)]n (3), (tma  =  trimesate, oba  =  4,4′-oxybis(benzoate)), have been prepared through hydrothermal reaction. They exhibit two different kinds of 1D helical structures. Compound 1 exhibits 1D helical structure. However, compounds 2 and 3 display 1D meso-helical structure.Display Omitted
Keywords: 2-(2-pyridyl)benzimidazole; Coordination polymer; Crystal structure; Photoluminescence;

A two-dimensional layered cadmium sulfide superlattice constructed from capped-supertetrahedral C1 clusters by Xiao-Li Yang; Jun Zhang; Shi-Bin Ren; Yi-Zhi Li; Wei Huang; Hong-Bin Du; Xiao-Zeng You (1337-1339).
A new two-dimensional layered cadmium sulfide framework MSF-5 based on a capped-supertetrahedral C1 cluster [Cd17S4(SPhMe-4)27(SH)]2− has been synthesized. MSF-5 possesses a 3-connected 63hcb net, in which each C1 cluster connects through Cd–S(PhMe-4)–Cd covalent bonds with three neighboring clusters to form a 2D superlattice with 6-membered rings. The 2D sheets stack over each other to form a 3D network. MSF-5 has high thermal stability and is a wide-gap semiconductor.A new two-dimensional layered cadmium sulfide framework MSF-5 based on a capped-supertetrahedral C1 cluster [Cd17S4(SPhMe-4)27(SH)]2− has been synthesized, which has high thermal stability and is a wide-gap semiconductor.Display Omitted
Keywords: Metal chalcogenide; CdS; Superlattice; Semiconductor; Crystal structure;

Reaction of uranium oxynitrate hexahydrate with 4, 4″-Dicarboxyl-(1,1′,3′,1″)-Terphenyl (H2L) by liquid diffusion method resulted in a complex {[UO2(L)(DMF)]·H2O} n . Single-crystal diffraction analysis shows that the uranyl ion is in a pentagonal bipyramid coordination environment. Five oxygen atoms of L2− ligands and DMF constructed the equatorial plane. Two oxygen atoms of uranyl occupy the two axial positions. The complex got the two-dimensional layered structure by π–π interactions. The thermal analysis verifies the component and the structure of the complex. The UV/vis measurement exhibits that the complex has strong absorption in the UV and visible region.Reaction of uranium oxynitrate hexahydrate with 4, 4″-Dicarboxyl-(1,1′,3′,1″)-Terphenyl (H2L) resulted in the complex [UO2(L)(DMF)] n •nH2O. UV–vis spectroscopic data exhibit that the complex has strong absorption in the UV and visible region.
Keywords: Uranium complex; Carboxylate ligand; Crystal structure; UV/vis absorption;

A chromotropic ferrocenyl chalcone with two pyrenyl groups (Fc-dPyr) is prepared and spectroscopically characterized. The X-ray structure analysis shows that the two pyrenyl groups are almost parallel to each other with a torsion angle of 5.57° and adopt a dimeric mode with a distance of 3.776 Å between them, ready to form an excimer. The solvatochromic fluorescence spectra indicate that the emission maxima observed in hydrogen-bonding donor (HBD) solvents (CHCl3, EtOH and MeOH) exhibit a strictly linear relationship with the normalized ET N value, while those in a non-HBD solvent (CH3CN) do not. The molecular chemosensor activity of Fc-dPyr is highly selective toward Fe(III) ions over Fe(II) ions. The fluorescence emission intensity of Fc-dPyr steeply decreases in the presence of Fe(III) ions as an oxidant, but not in the presence of Fe(II) ions.A chromotropic ferrocenyl chalcone with two pyrenyl groups (Fc-dPyr) is prepared and investigated. The solvatochromic fluorescence spectra are linearly proportional to the polarity (ET N value) of hydrogen-bonding donor (HBD) solvents, and the fluorescence intensity of Fc-dPyr shows a selectivity on the Fe(III) ions over the Fe(II) ions.Display Omitted
Keywords: Ferrocenyl chalcone; Pyrene; Solvatochromism; Fe(III)/Fe(II) sensor; Fluorescence;

Two 2D metal–organic frameworks based on 2,2′-bibenzimidazole ligand with (6,3) net topology by Shen Lin; Li-Juan Chen; Hui-Hong Xu; Jiang-Bo Su; Hua Huang (1347-1349).
Two 2D metal–organic frameworks (MOFs), {[Zn4(Hbbim)4(bbim)2] 2H2O}n (1) and [Cd2(Hbbim)2(bbim)]n (2) (H2bbim = 2,2′-bibenzimidazole) were obtained by solvothermal reaction and characterized by single crystal X-ray diffraction analysis. Different metal ions, Cd(II)/Zn(II), adopt very different coordination geometries though two title compounds both have a 2D honeycomb network with (6,3) topology. The frameworks of compounds 1 and 2 are stable below 360 °C and 475 °C, respectively. Solid-state luminescent spectroscopy of compound 2 exhibits an emission peak at 407 nm.Two 2D honeycomb network structure based on the connectivity of 2,2′-bibenzimidazole and corresponding d10 metal ions(Zn2+, Cd2+) with the same (6,3) topology but different coordination geometries.Display Omitted
Keywords: Metal–organic frameworks; 2,2′-Bibenzimidazole; Solvothermal reaction; Cadmium; Zinc; Luminescence;

Two new compounds were prepared and characterized structurally. Two anions coordinate to a Ln4-ring from two sides forming a polymeric anion, the polymeric anions connects the Ln1 ions, creating two dimensional structure. Two compounds show a very weak antiferromagnetic interaction.Display Omitted
Keywords: Magnetic property; Crystal structure; Keggin polyoxometalate; Lanthanide-organic complexes; Two-dimensional structure;

A new polyoxoniobate with NbIVO8 center and Cu24 core by Huaqiao Tan; Weilin Chen; Ding Liu; Yangguang Li; Enbo Wang (1354-1356).
A new polyoxoniobate with NbIVO8 center and Cu24 core K12Na[H23NbIVO8Cu24(Nb7O22)8]·81H2O (1) has been synthesized by the reaction of K7HNb6O19·13H2O with Cu(CH3COO)2·H2O in the presence of NbIVO2, and characterized by elemental analyses, IR spectrum, TG analysis, magnetic property and single-crystal X-ray diffraction. The structure analysis reveals that the polyoxoanion is composed of one NbIVO8 cube-like unit, 24 copper centers and eight [Nb7O22]9− fragments. The magnetic investigation shows that compound 1 exhibits antiferromagnetic interactions.A new polyoxoniobate with NbIVO8 center and Cu24 core K12Na[H23NbIVO8Cu24(Nb7O22)8]·81H2O (1) has been synthesized. The polyoxoanion is composed of one NbIVO8 cube-like unit, 24 copper centers and eight [Nb7O22]9− fragments.Display Omitted
Keywords: Polyoxoniobate; Copper; Crystal structure; Magnetic property;

Ionothermal synthesis and crystal structure of a new layered nickel(II) diphosphate, DRM-1 by Ying Wei; Hermann Gies; Zhijian Tian; Bernd Marler; Yunpeng Xu; Lei Wang; Huaijun Ma; Renyan Pei; Keda Li; Bingchun Wang (1357-1360).
A new layered ammonium nickel(II) diphosphate, (NH4)2[Ni3(P2O7)2(H2O)2], has been synthesized ionothermally in the ionic liquid 1-butyl-3-methyl imidazolium bromide and characterized by powder X-ray diffraction, elemental analysis, scaning electron microscopy, thermogravimetry etc. The results of the characterization show that the crystal adopts the monoclinic space group P21/a with the lattice constants a = 9.23529(2) Å, b = 7.98489(2) Å, c = 9.40772(2) Å, β = 100.2608(2)° and Z = 2. Its structure consists of chains of cis- and trans-edge-sharing [NiO6]-octahedra linked via [P2O7] units to form layers of [Ni3(P2O7)2(H2O)2]2− in the ab plane. Adjacent layers are separated in the c-direction by ammonium ions.A new layered nickel(II) diphosphate, DRM-1, has been synthesized ionothermally using ionic liquid 1-butyl-3-methylimidazolium bromide as the reaction solvent.Display Omitted
Keywords: Ionothermal synthesis; Ionic liquids; Nickel diphosphate; Open-framework; Layered structure;

Modified thiourea was used as the ligand for the synthesis of three novel coordination complexes, basing on its increased H-bond donor ability of the NH group and decreased H-bond acceptor ability of the C = S bond. Complex 1 is the first 3D network with 1D rod SBU and 2D surface SBU based on the long biscarboxylate ligand; Complex 2 has a 2D layer constructed by 1D chains via H-bonds, which shows a “plywood-like array” with a new AABB type; Complex 3 is a 3-fold interpenetrating 5-connected net with the rare 4664 topology.Complex 1 is the first 3D network which has 1D rod SBU and 2D surface SBU based on the long biscarboxylate ligand. Complex 2 shows a “plywood-like array” with a new AABB type. Complex 3 is the first example of 3-fold interpenetrating 5-connected net with a rare 4664 topology.Display Omitted
Keywords: Coordination polymer; Rod SBU; Surface SBU; H-bonds; 5-connected; 4664 topology;

Formations of a nonanuclear peroxo molybdate and its heptanuclear precursor by Quan-Liang Chen; Rong-Hua Zhang; Zhao-Hui Zhou; Hui-Lin Wan (1366-1369).
Coupling reaction of peroxo heptanuclear and dinuclear molybdenum complexes K6[Mo7O22(O2)2]·9H2O (1) and K2[Mo2O3(O2)4(H2O)2]·2H2O (2) results in the formation of a nonanuclear peroxo molybdate K8[Mo9O25(O2)6]·9H2O (3) in a weak acidic solution, which is promoted by the existence of lactic acid. The activation of peroxo group in compound 3 shows obvious O–O bond activation in comparison with 1, which is based on structural data and infra-red analyses.Formations of a nonanuclear peroxo molybdate and its heptanuclear precursor. Coupling reaction of peroxo heptanuclear and dinuclear molybdates result in the formation of a nonanuclear peroxo molybdate K8[Mo9O25(O2)6]·9H2O. The latter shows activation of peroxo groups in heptameric unit.Display Omitted
Keywords: Heptamolybdate; Nonamolybdate; Peroxo; Molybdenum complex; Lactic acid;

Display Omitted
Keywords: Pincer ligand; Ruthenium(II); Synthesis; Crystal structure; Catalytic oxidation; Alcohols;