Inorganic Chemistry Communications (v.11, #4)

Contents List (iii-ix).

The H-bonding association among eight lattice water molecules forms a 2-D water sheet consisting of the fused eighteen-membered water rings. The water layer has the two kinds of three-connected nodes occupied by O3w and O8w, respectively.The unprecedented 2-D hydrated proton consisting of the fused H+(H2O)18 ring has been found in Et4N · H+(H2O)8  · [Mo3O4(C2O4)3(H2O)3] (1). The proton has been found to be located around the disordered three-connected nodes of the water sheet as revealed by the unusually short O⋯H+⋯O bonds. The protonated water layer is supported by the H-bonds between the ring water molecules and the host framework constructed from the triangular trimolybdenum(IV) cluster dianion, [Mo3O4(C2O4)3(H2O)3]2−.
Keywords: Hydrated proton; Water sheet; H-bonds;

Two new microporous MOFs were constructed from the infinite rod-like Mn-O-C SBUs, and topology analysis suggests the pcu and sra net for them.Herein, we report two microporous MOFs, viz. Mn3(1,4-BDC)3(μ-DMF)2 (1), and Mn4(1,3-BDC)42-DMF)2  · (DMF)2 (2). Both 1 and 2 are constructed from the Mn–O–C rod-like SBUs and afford the irregular rhombic channels occupied by coordinated or free DMF molecules. The topology analysis suggests the pcu (also named α-Po) net for1 and sra (also named Al in SrAl2) net for 2. Moreover, the 1D Fisher mode is applied to analysis the experimental magnetic data, resulted in the J  =− 1.12 cm−1, θ  = 0.15 K, g  = 2.0 for 1 and J  =− 2.07 cm−1, θ  = 0.21 K, g  = 1.98 for 2, which suggests the antiferromagnetic interactions within the Mn–O–C rod and inter-chain ferromagnetic interactions (1,4-BDC = 1,4-benzenedicarboxylate, 1,3-BDC = 1,3-benzenedicarboxylate, J, g, and θ parameter are magnetic coupling parameter, Zeeman factor and the inter-chain interactions, respectively).
Keywords: Solvothermal synthesis; pcu net; sra net; Rod-like SBU; Micorporous MOF;

The reaction of [Mo(CN)8]4− with {Ni(Me6-[14]ane-N4)}2+ (Me6-[14]ane-N4  = 5,7,7,12,14,14-hexamethyl-1,4, 8,11-tetraazacyclotetradecane) led to a new three-dimensional cyano-bridged bimetallic assembly {Ni(Me6-[14]ane- N4)}2[Mo(CN)8] · 12H2O (1), which was characterized by IR, elemental analysis, ICP, TGA and SC-XRD. Magnetic behavior of complex 1 showed a weak antiferromagnetic interaction between Ni2+ ions through the diamagnetic [W(CN)8]4− bridges.The reaction of [Mo(CN)8]4− with {Ni(Me6-[14]ane-N4)}2+ (Me6-[14]ane-N4  = 5,7,7,12,14,14-hexamethyl-1, 4,8,11-tetraazacyclotetradecane) led to a new three-dimensional cyano-bridged bimetallic assembly {Ni(Me6-[14]ane- N4)}2[Mo(CN)8] · 12H2O (1), which was characterized by IR, elemental analysis, ICP, TGA and SC-XRD. Magnetic behavior of complex 1 showed a weak antiferromagnetic interaction between Ni2+ ions through the diamagnetic [W(CN)8]4− bridges.
Keywords: Octacyanomolybdate; Nickel complex; Crystal structure; Magnetic properties;

Two new extended lead(II) coordination polymers [Pb(2,2′-bipy)(H2O)(NO3)]2(bipd)(NO3)2 (1) and [Pb(Hpcih)]2(NO3)2(H2O) (2), with interesting structural motifs have been synthesized by solvothermal method. The coordination number of Pb2+ ion in both complexes is four with the stereo-chemically active lone pair, resulting in the hemidirected geometry. The Pb2+ ions complete their coordination spheres by so-called secondary bonds to O and N atoms with the holodirected geometry (PbN3O6 for 1 and PbN4O5 for 2), and produce two different extended structures, namely a pseudo 1-D zigzag chain in 1 and a pseudo 3-D network in 2.Two novel lead(II) complexes with bridging Schiff-base ligands, [Pb(2,2′-bipy)(H2O)(NO3)]2(bipd)(NO3)2 (1) and [Pb(Hpcih)]2(NO3)2(H2O) (2) (2,2′-bipy = 2,2′-bipyridine, bipd = 1,4-bis(3-pyridyl)-2,3-diazo-1,3-butadiene, Hpcih = 2-pyridinecarbaldehyde isonicotinoylhydrazone) have been synthesized by solvothermal method and structurally characterized. The coordination number of Pb2+ ion in both complexes is four with the stereo-chemically active lone pair, resulting in the hemidirected geometry. The Pb2+ ions complete their coordination spheres by so-called secondary bonds to O and N atoms with the holodirected geometry (PbN3O6 for 1 and PbN4O5 for 2), and produce two different extended structures, namely a pseudo 1-D zigzag chain in 1 and a pseudo 3-D network in 2. The thermal stability of complexes 1 and 2 was investigated by thermogravimetric measurements.
Keywords: Lead(II) complex; Bridging Schiff-base; Solvothermal synthesis; Hemidirected and holodirected;

Two new 3D coordination frameworks from 4-(1H-tetrazol-5-yl) benzoic acid were prepared. Two types of coordination modes of 4-TZBA2− ligand are found in these two compounds. The non-linear optical (NLO) activity of compound 2 shows that different assembly can lead to different function although the assembly has the same metal and ligand. The luminescent properties show that the emissions of 1 and 2 can be assigned to the ligand-to-metal charge transfer (LMCT), indicating that the emission wavelength and the intensity of the organic materials can be affected by metal coordination. All the results indicated that the functional materials can be obtained by adjusting the assembly on the basis of structure of the ligand.The coordination polymers [Mn(4-TZBA2−)(H2O)2] (1) and [Mn4(4-TZBA2−)4(μ2-H2O)2(H2O)(py)] (2) (py = pyridine) were prepared by the treatment of Mn(ClO4)2  · 6H2O with 4-(1H-tetrazol-5-yl) benzoic acid (H2(4-TZBA)) under hydrothermal conditions. Compound 2 has nanosize triangular channels with a dimension of 11.924 × 11.686 × 14.835 Å, in which guest water molecules are encapsulated. Compound 1 and 2 show strong fluorescence at room temperature in the solid state and compound 2 exhibits a second-order coefficient about 0.3 time that of KDP.
Keywords: Synthesis; Structure; Tetrazolate; Homochiral; Luminescence; Non-linear optics (NLO);

One left-handed homo-chiral 3-D metal–organic open framework hosting supramolecular left-handed methanol helices and one two-fold interpenetrated 3-D supramolecular framework have been constructed and structurally characterized.The self-assembly of 1,3,4-thiadiazole-2,5-di-4-pyridyl (L 1), 4,4′-dipyridyl (L 2) with Zn(II), Cu(II) salts afforded one unusual coordination polymer with left-handed homo-chiral 3-D open MOFs in which supramolecular left-handed methanol helices were selectively formed, and one 2-D coordination polymer where two-fold interpenetrated 3-D supramolecular frameworks were constructed by hydrogen bonds.
Keywords: Metal–organic frameworks; Interpenetrating; Chiral; Angular ligand;

We demonstrate a novel hydroxylation reaction of iron(II) benzoato complexes (2a2c) with molecular oxygen without any reducing agents to yield hydroxylated complexes (3a3c). This coordinate benzoate ion can be removed to make a novel iron(III) complex (4), whose ligand has two minus charge.A novel oxygen insertion reaction by molecular oxygen into an aromatic C–H bond in benzoato iron(II) complexes [FeII{HB(3-Ph-5-Mepz)3}(η1-O2CC6H4-p-X)(3-Ph-5-MepzH)] (2a (X = Cl), 2b (X = H), and 2c (X = OMe)) is described. The structures of the hydroxylated complexes ▪ (3a (X = Cl), 3b (X = H), and 3c (X = OMe)) were determined by X-ray crystallography and other spectroscopic characterizations were performed; one of the phenyl rings in the hydrotris(pyrazolyl)borate ligand was hydroxylated. A new purple colored iron(III) complex ▪ (4), which was obtained by the reaction of 3a with base, is also characterized.
Keywords: Iron complex; Hydrotris(pyrazolyl)borate; Hydroxylation; Crystal structure; Model complex;

A 1D flexible zigzag coordination polymer, {[Zn(bac)2(bpp)] · 1.5H2O} n (1) (bac = 1-benzoylacetone, bpp = 1,3-bis(4-pyridyl)propane), has been synthesized and structurally characterized. The zigzag chains in two different directions are entangled to generate a 2D interwoven network, which is stabilized by hydrogen bonding interactions.A 1D flexible zigzag coordination polymer, {[Zn(bac)2(bpp)] · 1.5H2O} n (1) (bac = 1-benzoylacetone, bpp = 1,3-bis(4-pyridyl)propane), has been synthesized by ambient evaporation of mixed solution and structurally characterized by single crystal X-ray diffraction. The zigzag chains in two different directions are entangled to generate a 2D interwoven network, which is stabilized by hydrogen bonding interactions. The powder X-ray diffraction (XRD) and thermogravimetric analysis (TGA) of 1 have also been studied.
Keywords: Crystal engineering; Coordination polymers; Zigzag chains; Interwoven networks;

The reaction of stoichiometric amount of FeCl3, Schiff-base ligand, NaBPh4 in CH3CN and 3,5-DTBC in CH3OH under O2 did produce a new μ-oxo-bridged hexanuclear iron(III) cluster with a spin ground state of S  = 5.The reaction of stoichiometric amount of FeCl3, Schiff-base ligand, NaBPh4 in CH3CN and 3,5-DTBC in CH3OH under O2 did produce a new μ-oxo-bridged hexanuclear iron(III) cluster [Fe6(L)23-O)2(μ-3,5-DTBC)4(μ-CH3O)2(Cl)2] (BPh4)2  · 2H2O (1) (L =  N,N-diethylenetriamino-bis(imidazolaldiminato) with a spin ground state of S  = 5.
Keywords: Iron(III) clusters; μ-Alkoxo–μ3-oxo–μ-catecholato bridges; Crystal structure; Magnetic properties; Mössbauer spectrum;

Ferrocenyl–azobenzene carboxylic acid labeled thymine PNA (Fc–Azo–T) monomer was synthesized and showed highly electrochemical and photochemical activity. The influence of isomerization to electrochemical properties was discussed.Ferrocenyl–azobenzene carboxylic acid was synthesized and used as electrochemically and spectroscopically active marker that was conjugated to thymine PNA monomer. Ferrocenyl–azobenzene labeled PNA monomer of thymine (Fc–Azo–T) shows highly electrochemical and photochemical activity. The detection limit of Fc–Azo–T can reach 10−6  M by using differential pulsed voltammogram (DPV), and the UV–vis limit is in the order 10−7  M in ethanol. Fc–Azo–T can undergo facile isomerization by photoirradiation. The results give great motivity for synthesizing ferrocenyl–azobenzene labeled PNA oligomers used as an effective electrochemical and photochemical probes.
Keywords: Peptide nucleic acid (PNA); Ferrocene; Azobenzene; Electrochemistry; Photochemistry;

Solvothermal synthesis and characterization of a lithium coordination polymer possessing a highly stable 3D network structure by Ying-Ya Liu; Jian Zhang; Li-Xian Sun; Fen Xu; Wan-Sheng You; Yi Zhao (396-399).
Solvothermal reaction of lithium perchlorate and 1,4-benzene dicarboxylate acid at 180 °C has resulted in a novel lithium coordination polymer Li2 (CO2–C6H4–CO2) with a remarkable high thermal stability up to 530 °C, which features a new 3D network containing two types of 6-membered ring and 18-membered dumbbell-like ring in view from different directions.Solvothermal reaction of lithium perchlorate and 1,4-benzene dicarboxylic acid at 180 °C has resulted in a novel lithium coordination polymer Li2 (CO2–C6H4–CO2), which is characterized by single crystal X-ray diffraction analysis, X-ray powder diffraction analysis, elemental analysis, TGA/DTA and IR spectra. The compound shows a remarkable high thermal stability up to 530 °C, features a new 3D network containing two types of 6-membered ring and 18-membered dumbbell-like ring in view from different directions.
Keywords: Metal–organic framework; Coordination polymer; Lithium; Solvothermal synthesis;

Four complexes with macrocyclic unit benzo-12-crown-4 or benzo-15-crown-5 have been synthesized. Introduction of Li+ and Na+ to the CH3CN solution of complexes result in a progressive enhancement of the fluorescence intensity and a hyperchromic effect of the UV–vis absorption.Two polypyridyl ligands 4′-(imidazo[4,5-f][1,10]phenanthrolin-2-yl)benzo-12-crown-4 (L1), 4′-(imidazo[4,5-f][1,10]phenanthrolin-2-yl)benzo-15-crown-5 (L2) and corresponding complexes [(bpy)2RuL1–2](PF6)2 (1, and 2) and [Ru(L1–2)3](PF6)2 (3, and 4) have been synthesized. These complexes show metal-to-ligand charge transfer absorption at 458–468 nm and emission at 585–592 nm. Binding ability of the complexes with Li+ and Na+ were investigated by fluorescence and UV–vis titration.
Keywords: Ru(II) complex; Benzocrown ether; Chemical sensor;

Two linearly arranged trinuclear silver complexes, [Ag3(L)2(CH3CN)](PF6)3 (L = 2,7-bis(alkylimidazolylidenyl)naphthyridine), have been characterized by NMR spectroscopy and X-ray diffraction analysis.Reactions of the imidazolium salts with Ag2O afforded trinuclear silver complexes [Ag3(L)2(CH3CN)](PF6)3 (L = 2,7-bis(alkylimidazolylidenyl)naphthyridine), which have been characterized by NMR spectroscopy and X-ray diffraction analysis. The complexes consist of linearly arranged Ag3 cores showing weak silver–silver interactions as evidenced by the short silver–silver contacts (3.10–3.24 Å). The complexes are intensely emissive in their solid states.
Keywords: Silver; Naphthyridine; N-heterocyclic carbene; Silver–silver interaction; Luminescence;

The reaction of (tht)AuCl (tht = tetrahydrothiophene) with the bulky phosphine ligand Ad2BnP yields [(Ad2BnP)2Au][AuCl2] (1, Ad = 1-adamantyl, Bn = benzyl) as the first example of a 1:1 chloro(phosphine)gold(I) complex having an ionic structure both in solution and solid state. For comparison, the analogous complex ( Ad 2 n BuP ) AuCl (2, n Bu =  n-butyl) has been synthesized and analysed by single crystal X-ray diffraction. In its crystal, it has a common rod-like structure known from R3PAuCl complexes with bulky phosphine ligands.The reaction of (tht)AuCl (tht = tetrahydrothiophene) with the bulky phosphine ligand Ad2BnP yields [(Ad2BnP)2Au][AuCl2] (1, Ad = 1-adamantyl, Bn = benzyl) as the first example of a 1:1 chloro(phosphine)gold(I) complex having an ionic structure both in solution and solid state. The crystal structure of 1 revealed that the Au(I) atom is linearly coordinated by the phosphorus atoms and effectively shielded from the surroundings by the bulky substituents of the phosphine ligand. For comparison, the analogous complex ( Ad 2 n BuP ) AuCl (2, n Bu =  n-butyl) has been synthesized and analysed by single crystal X-ray diffraction. In its crystal, it has a common rod-like structure known from R3PAuCl complexes with bulky phosphine ligands.
Keywords: Gold; Bulky phosphine ligands; Gold chloride; π-Gold interactions;

The hydrazinium cations N 2 H 6 2 + / N 2 H 5 + form ion pairs with [Pt(CN)4]2. Outer-sphere charge transfer excitation (PtII  →  N 2 H 6 2 + / N 2 H 5 + ) induces an oxidative addition: N 2 H 6 2 + / N 2 H 5 + Pt(CN)4 2  → [PtIV(CN)4(NH3)2] and [Pt(CN)4(NH3)(NH2)], respectively.The hydrazinium cations N2H6 2+/N2H5 + form ion pairs with [Pt(CN)4]2−. Outer-sphere charge transfer excitation (PtII  →  N 2 H 6 2 + / N 2 H 5 + ) induces an oxidative addition: N 2 H 6 2 + / N 2 H 5 + Pt ( CN ) 4 2 -  → [PtIV(CN)4(NH3)2] and [Pt(CN)4(NH3)(NH2)], respectively.
Keywords: Charge transfer; Photochemistry; Platinum; Hydrazinium; Oxidative addition;

Intraligand fluorescence and phosphorescence of tris(pyrazolyl) hydridoborate complexes by Horst Kunkely; Valeri Pawlowski; Andreas Strasser; Arnd Vogler (415-417).
The complexes GdTp3 and PPh3AgTp with Tp = Hydridotris(1-pyrazolyl)borate in the solid state are characterized by rather similar luminescence spectra which consist of a fluorescence near 390 nm and a phosphorescence near 480 nm. These emissions originate from a Tp ππ∗ IL singlet and triplet, respectively. Owing to the heavy-atom effect of Gd and Ag the phosphorescence appears also at rt.The complexes GdTp3 and PPh3AgTp with Tp = Hydridotris(1-pyrazolyl)borate in the solid state are characterized by rather similar luminescence spectra which consist of a fluorescence near 390 nm and a phosphorescence near 480 nm. These emissions originate from a Tp ππ∗ IL singlet and triplet, respectively. Owing to the heavy-atom effect of Gd and Ag the phosphorescence appears also at rt.
Keywords: Fluorescence; Phosphorescence; Silver(I); Gadolinium(III); Hydrotris(1-pyrazolyl)borate;

High nuclearity Cu11 and Cu6Ln2 (Ln = Eu, Gd) cluster compounds with unusual structural features and magnetic behaviors have been synthesized under solvothermal conditions based on di(pyridin-2-yl) methanone [(py)2CO] derivatives.High nuclearity Cu11(1) and Cu6Ln2 (Ln = Eu, 2; Gd, 3) cluster compounds with unusual structural features have been synthesized under solvothermal conditions based on di(pyridin-2-yl)methanone [(py)2CO] derivatives. Magnetic susceptibility measurement for 1 and 3 are consistent with the existence of anti-ferromagnetic interaction.
Keywords: Solvothermal synthesis; Copper-lanthanide clusters; Di(pyridin-2-yl)methanone;

Lead(II)-induced formation and coordination of 3,4-dihydro-3-thioxo-1,2,4-triazin-5(2H)-one by José S. Casas; Eduardo E. Castellano; Javier Ellena; María S. García-Tasende; Agustín Sánchez; José Sordo; Ángeles Touceda (423-426).
Lead(II)-induced cyclization of a α-ketoester thiosemicarbazone leads to the formation of a triazinethionate complexCyclization of n butyl glyoxylate thiosemicarbazone (HBuTSC) under reflux in the presence of Pb(OAc)2 led to the formation of the complex [Pb(HTz)2] (H2Tz = 3,4-dihydro-3-thioxo-1,2,4-triazin-5(2H)-one), which after recrystallization from DMSO afforded the polymer [Pb(Tz)] n , the first example of a Tz2− metal complex.
Keywords: Lead(II) complexes; Triazinethiones; Cyclization of thiosemicarbazones; X-ray diffraction; NMR spectroscopy;

A novel octanuclear copper(II) compound: Synthesis, crystal structure and magnetic properties by Sujittra Youngme; Nanthawat Wannarit; Tawun Remsungnen; Chaveng Pakawatchai; Narongsak Chaichit; Chainarong Engkagul; Gerard A. van Albada; Jan Reedijk (427-432).
The crystal structure of a novel octanuclear copper(II) complex containing the bidentate 1,10-phenanthroline ligand (phen) with cooperative carbonato and hydroxido bridging ligands, [Cu8(phen)123-OH)2(μ-OH)23-CO3)2](CF3SO3)8(DMF)2(H2O)0.5 (1) is described. The di-μ-hydroxidocopper(II) species play an important role for the apparent ferromagnetic interaction with the Cu–OH–Cu angles (θ) of 95.8(2)° and 93.5(1)°. The intra- and intermolecular ππ stacking interactions between pyridine groups of phen ligand stabilize the lattice structure. The spectroscopic properties (IR, reflectance and EPR spectra) and the magnetic susceptibility data of this compound are investigated.The crystal structure of a novel octanuclear copper(II) complex containing the bidentate 1,10-phenanthroline ligand (abbreviated as phen) with cooperative carbonato and hydroxido bridging ligands, [Cu8(phen)123-OH)2(μ-OH)23-CO3)2](CF3SO3)8(DMF)2(H2O)0.5 (1) (when DMF =  N,N-dimethylformamide) is described. Compound 1 consists of two symmetry-related di-μ-hydroxido-bis(1,10-phenanthroline)copper(II) groups which held together by long Cu–O(H) bonds, creating a Cu2(OH)2 core of a tetranuclear hydroxido-bridged copper(II) unit, further coordinated with trans-axially at Cu(3) and Cu(3)A by [μ3-carbonato-tetrakis(phen)dicopper(II)] moieties. The di-μ-hydroxidocopper(II) species play an important role for the apparent ferromagnetic interaction with the Cu–OH–Cu angles (θ) of 95.8(2)° and 93.5(1)°. The spectroscopic properties (IR, reflectance and EPR spectra) and the magnetic susceptibility data of this compound are investigated and compared with other related polynuclear copper(II) compounds.
Keywords: Carbonate chemistry; Copper(II) complexes; Octanuclear; Crystal structure; EPR; Magnetism;

Two amidine Co(III) complexes, [Co(HL) (H2L)](ClO4)2 (1) and [Co(HL)2 (Py)2](ClO4) · CH3CN (2), have been synthesized by mixture of Cobalt perchlorate, 2-amino-1,3,4-thiadiazole and pyridine in acetonitrile solution. There existed a redox process of cobalt from +2 to +3 oxidation state and a metal-induced coupling of 2-amino-1,3,4-thiadiazole with acetonitrile to give amidine in the reaction system.A planar square Co(III) complex, [Co(HL)(H2L)](ClO4)2 (1) (H2L =  N-(1,3,4-thiadiazol-2-yl)acetimidamide, C4H6N4S), was synthesized by mixing Co(II) salt with 2-amino-1,3,4-thiadiazole in acetonitrile, and the subsequent addition of pyridine led to an octahedral Co(III) complex, [Co(HL)2(Py)2](ClO4) · CH3CN (2) (Py = pyridine). To mix 2-amino-1,3,4-thiadiazole, pyridine and cobalt perchlorate directly into acetonitrile can also afford complex 2 in higher yield. Complexes 1 and 2 have been characterized by X-ray single crystal diffraction and cyclic voltammetry, and the reaction mechanism has been discussed.
Keywords: 2-Amino-1,3,4-thiadiazole; Amidine complex; Cobalt complex; Crystal structure; Cyclic voltammetry;

The complex [Cu(tacp)(H2O)]2[Cu(μ2-C2O4)2(ClO4)2] (tacp = 1,4,8,12-tetraazacyclopentadecane) was synthesized and structurally characterized. It exhibits weak antiferromagnetic coupling and two types of coordination modes were found for the bridging oxalate.A novel tricopper bridged oxalato complex with the structural formula [Cu(tacp)(H2O)]2[Cu(μ2-C2O4)2(ClO4)2] (1) where tacp = 1,4,8,12-tetraazacyclopentadecane was synthesized. The complex was characterized by X-ray crystallography and by spectroscopic techniques (IR and visible). The magnetic properties were also measured at variable temperatures (300–2 K). In this compound each oxalate is acting as a bridging ligand between two Cu2+ ions, where two types of coordination modes are found for the oxalate: monodentate and bidentate fashions. The magnetic coupling between the Cu–Cu centers is very weak antiferromagnetic (the singlet–triplet energy coupling J  = −0.9 cm−1) and is in full agreement with the structural results.
Keywords: Copper(II) complexes; Polynuclear complexes; Oxalato-bridged; Crystal structure; Magnetic properties;

Water molecules associated with chloride anions form supramolecular hydrogen-bonded self-assembled tapes made of fused five- and six-membered rings, [(H2O)3Cl(OH)] and [(H2O)4Cl(OH)], serving as a template in the crystal structure of dinuclear {[Cu(dien)(μ-OH)]+Cl}2  · 3H2O.Water molecules in association with chloride anions form supramolecular self-assembled tapes made of fused five- and six-membered rings, [(H2O)3Cl(OH)] and [(H2O)4Cl(OH)], serving as a template in the crystal structure of dinuclear {[Cu(dien)(μ-OH)]+Cl}2  · 3H2O, based upon a Cu2(μ-OH)2 central moiety.
Keywords: Crystal structure; Supramolecular self-assembly; Water–chloride assembly; Hydrogen bonds; Copper(II) complexes; Hydroxo-bridged dimer;

A new 1D coordination polymer [Cu(trtr)Cl2] n  · 2nH2O (trtr = 4,4′-bi-1,2,4-triazole) was synthesized from the solution reaction of CuCl2 and trtr. The polymer is constructed by a inorganic skeleton chain [CuCl2] n with trtr anchoring on both sides like wing. The title compound features a dual-peak emission at 420 and 439 nm originating, respectively, from the π–π intraligand transition and LMCT. The optical gap of 2.45 eV suggests the compound possesses semiconducting character.A new 1D coordination polymer [Cu(trtr)Cl2] n  · 2nH2O (trtr = 4,4′-bi-1,2,4-triazole) was synthesized from the solution reaction of CuCl2 and trtr. The polymer is constructed by an inorganic skeleton chain [CuCl2] n with trtr anchoring on both sides like wing. The lattice water plays a significant role in the construction of the 3D super-molecular architecture by forming hydrogen bondings between trtr and water molecules. The fluorescence spectrum of the title compound features a dual-peak at 420 and 439 nm originating, respectively, from the π–π intraligand transition and LMCT. Diffuse reflectance spectrum of the compound reveals the presence of optical gap of 2.45 eV, suggesting that the compound possesses semiconducting character.
Keywords: 1,2,4-Triazole; Crystal structure; Diffuse reflectance spectrum; Fluorescence;

Synthesis, crystal structure, and fluorescence studies of (1-naphthyl)(pyridyl)urea metal complexes by Xiaojuan Huang; Yana Xia; Hongrui Zhang; Zhenzhong Yan; Yu Tang; Xiao-Juan Yang; Biao Wu (450-453).
Three metal complexes [ML 2Cl2(MeOH)2] (M = Cu (1), Co (2) and Ni (3); L  =  N-(1-naphthyl)-N′-(3-pyridyl)urea) have been synthesized, which feature a 2D network formed by N–H⋯Cl hydrogen bonding. The fluorescence studies show a red-shift or quenching of the emission upon metal coordination.Three supramolecular complexes, [ML 2Cl2(MeOH)2] (M = Cu (1), Co (2) and Ni (3); L  =  N-(1-naphthyl)-N′-(3-pyridyl)urea) have been synthesized and characterized. X-ray single-crystal diffraction analyses revealed a 2D network for the isomorphous complexes 1, 2 and 3 formed by intermolecular N–H⋯Cl hydrogen bonding and π–π stacking interactions. The fluorescent properties of the complexes have been investigated. While complexes 2 and 3 showed a red-shifted fluorescence emission in the solid-state compared to L, complex 1 displayed a quenching of the fluorescence.
Keywords: N-(1-Naphthyl)-N′-(3-pyridyl)urea; Hydrogen bonding; Metal complex; Fluorescence;

The first tridecanuclear nickel(II) cluster: [Ni13(OH)6(O2CMe)8(btaO)12(H2O)6(nPrOH)4] (btaOH = 1-hydroxybenzotriazole) by Constantina Papatriantafyllopoulou; Eleanna Diamantopoulou; Aris Terzis; Nikolia Lalioti; Vassilis Tangoulis; Spyros P. Perlepes (454-460).
The 1:1 Ni(O2CMe)2·4H2O/1-hydroxybenzotriazole reaction system in propanol gives a tridecanuclear cluster which has the shown {Ni133-OH)63-ONNNR)12}8+ core; the compound is the biggest metal 1-hydroxybenzotriazole cluster discovered to date and the first Ni13 complex. The μ3-OH groups can be replaced by end-on, triply bridging N 3 - ligands.The reaction of 1-hydroxybenzotriazole (btaOH) with Ni(O2CMe)4  · 4H2O in nPrOH has led to the [Ni13(OH)6(O2CMe)8(btaO)12(H2O)6(nPrOH)4] (1) cluster; compound 1 is the first structurally characterized tridecanuclear nickel(II) cluster and the biggest metal/btaOH or btaO cluster discovered to date. The centrosymmetric molecule contains the {Ni133-OH)63-ONNNR)12}8+ core (R– = C6H4–) and is characterized by competitive antiferromagnetic exchange interactions within its pentanuclear subunits containing the μ3-OH bridges. The reaction of 1 with an excess of N 3 - ions in refluxing MeOH has led to the azido-bridged product [Ni13(N3)6(O2CMe)8(btaO)12(MeOH)10] (2).
Keywords: 1-Hydroxybenzotriazolate metal complexes; Magnetic properties; Nickel(II); Tridecanuclear clusters;

Unexpected formation of a new nitrosylrhenium(II) complex from oxorhenium(V) by Irvin Booysen; Thomas I.A. Gerber; Peter Mayer (461-464).
A novel nitrosylrhenium(II) complex salt, [Re(NO)BrL2(PPh3)2](ReO4) (H2L2  = 2-amino-5-(triphenylphosphino)phenol), was prepared from trans-[ReOBr3(PPh3)2] and the rhenium-induced ligand conversion of 2-(benzoxazol-2-yl)benzamine. This is the first example of a complex containing the triphenylphosphonium-amidophenolate ligand L2, formed by the nucleophilic attack of a PPh3 on a coordinated amidophenolate ring.A new nitrosylrhenium(II) complex salt, [Re(NO)BrL2(PPh3)2](ReO4) (H2L2  = 2-amino-5-(triphenylphosphino)phenol), has been synthesized and characterized by single crystal X-ray structure determination and IR spectroscopy. This is the first example of a complex containing the triphenylphosphonium-amidophenolate ligand L2, formed by the nucleophilic attack of a PPh3 on a coordinated amidophenolate ring.
Keywords: Nitrosylrhenium(II); X-ray crystallography; IR; Phosphonium-amidophenolate;