Inorganic Chemistry Communications (v.14, #12)

Contents List (iii-xi).

Structure and magnetic properties of hexanuclear 3d–4f clusters with {MnIII 2LnIII 4} (Ln = Sm, Eu, Gd, Tb, Dy, Ho) core by Jürgen Feuersenger; Denis Prodius; Valeriu Mereacre; Rodolphe Clérac; Christopher E. Anson; Annie K. Powell (1851-1854).
Reactions between hexanuclear manganese pivalate with lanthanide salts (chlorides or nitrates), in the presence of potassium hydroxide, 2-pyridylmethanol and sodium azide leads to formation of a new family of hexaheteronuclear manganese–lanthanide clusters.Reactions between hexanuclear manganese pivalate with lanthanide salts (chlorides or nitrates), in the presence of potassium hydroxide, 2-pyridylmethanol and sodium azide leads to formation of new family of hexaheteronuclear manganese–lanthanide clusters.Display Omitted► An effective approach to access of new hexanuclear 3d-4f clusters. ► Weak antiferromagnetic intermolecular interactions. ► Molecular construction of manganese–lanthanide complexes with different nuclearity.
Keywords: Manganese–lanthanide clusters; Antiferromagnetic interaction;

Two novel metal–organic frameworks of [M3(ptz)2(N3)4(H2O)2] (M = Zn(1), Cd(2)) (ptz = 5-(4-pyridyl)tetrazolate) have been prepared hydro(solvo)thermally by reactions of 4-cyanopyridine and excess NaN3 in the presence of zinc and cadmium chloride, respectively. The overall structure motif of complexes 1 and 2 show pillared layered frameworks and feature an unprecedented 3-nodal network with (3,5,6)-connectivity. The layer is of particular interest as it is constructed by μ1,1–N3 and μ1,1,3–N3 bridging modes, simultaneously. Furthermore, the solid fluorescent properties and TGA were studied.Two isostructural complexes feature a novel 3D pillared layered structure which represents an uncommon example of a (3,5,6)-connected net with Schläfli symbol of (4.53.6.73.8.9)(42.54.62.74.93)(4.7.8)(4.5.6).Display Omitted► Two pillared layered three-dimensional complexes have been synthesized. ► The layer is constructed by μ1,1–N3 and μ1,1,3–N3 bridging modes, simultaneously. ► The frameworks exhibit 3-nodal network with (3,5,6)-connectivity topology. ► Complexes 1 and 2 exhibit strong photoluminescence at room temperature.
Keywords: Hydro(solvo)thermal synthesis; In situ; Azide; (3,5,6)-connected; Luminescence;

A self-assembled non-interpenetrating cubic diamondoid coordination polymer of hexamine with linear dicopper spacer: Structural and magnetic studies by Shantanu Hazra; Biswarup Sarkar; Subrata Naiya; Michael G.B. Drew; Joan Ribas; Carmen Diaz; Ashutosh Ghosh (1860-1863).
Structural characterization of a new self assembled coordination polymer of CuII, hexamine (hmt) and benzoate (OBz), [Cu4(OBz)8(hmt)]n (1), reveals that it is a cubic non-interpenetrating diamondoid network formed by the coordination of the μ4-hmt ligand to a linear [Cu2(OBz)4] spacer. The magnetic study reveals that the Cu(II) ions are antiferromagnetically coupled (J = − 323.5 cm−1) through the synsyn carboxylate bridges.A new self-assembled cubic diamondoid coordination polymer of Cu2(OBz)4 and μ4-hexamine (hmt), [Cu4(OBz)8(hmt)]n in which the Cu(II) ions are antiferromagnetically coupled through the syn–syn carboxylate bridges is reported.Display Omitted► A new self assembled coordination polymer of CuII, hexamine and benzoate. ► The first cubic non-interpenetrating diamondoid network of μ4-hmt and linear [Cu2(OBz)4] spacer. ► The antiferromagnetic coupling of Cu(II) through the synsyn carboxylate bridges.
Keywords: Copper(II); Benzoate; Hexamine; Crystal structure; Magnetic properties;

Selective “turn-on” fluorescent chemosensors for Cu2+based on anthracene by Meng Lu; Xiang Ma; Yuan-Jie Fan; Chen-Jie Fang; Xiao-Fei Fu; Ming Zhao; Shi-Qi Peng; Chun-Hua Yan (1864-1867).
Simple PET chemosensors based on anthracene show a selective turn-on fluorescence sensing for Cu2+. The flexible receptor is favorable for turn-on sensing due to chelation enhanced fluorescence. Interestingly, the turn-on fluorescence sensing for Cu2+ is hardly disturbed by the competitive cations and other highly prevalent species in biological and environmental systems, implying a potential in the biological and environmental applications.Anthracene derivatives, as fluorescent chemosensors, show high selectivity for sensing copper ion in a turn-on fashion, and the fluorescence enhancement is hardly disturbed by the other relevant ions.Display Omitted► The anthracene derivatives show a turn-on fluorescence sensing for Cu2+. ► The mechanism of PET chemosensors is chelation enhanced fluorescence effect. ► The turn-on sensing for Cu2+ is hardly disturbed by the other cation.
Keywords: Cu2+; Fluorescent chemosensor; Anthracene; Turn-on sensing;

Specific molecular container for dioxane by Jungmin Ahn; Kyung Hwan Park; Tae Hwan Noh; Ok-Sang Jung (1868-1870).
Metallacyclodimeric complex of [(Me4en)Pd(L)]2(PF6)4 (Me4en =  N,N,N′,N′-tetramethylethylenediamine; L = 1,3-bis(4-pyridyl)tetramethyldisiloxane) is a sensitive container for dioxane via appropriate size effect. The equilibrium between the “included” and “free” dioxane species has been monitored by temperature-dependent 1H NMR spectra.Display Omitted► Metallamacrocyclodimeric complex, [(Me4en)Pd(L)]2(PF6)4 (L = 1,3-bis(4-pyridyl)tetramethyldisiloxane) has been synthesized. ► This metallacyclic system is the first exact dioxane container via the appropriate size effect. ► The equilibrium of a “free” and “included” dioxane was investigated by means of variable-temperature 1H NMR spectra.
Keywords: 1,3-Bis(4-pyridyl)tetramethyldisiloxane; 1,4-Dioxane recognition; Host–guest chemistry; Metallacyclodimer; Palladium(II) complex;

Characterization of an unprecedented (ethanol)4 cluster in a novel photoluminescent silver(I) coordination polymer by Di Sun; Yun-Hua Li; Fu-Jing Liu; Hong-Jun Hao; Rong-Bin Huang; Lan-Sun Zheng (1871-1875).
An unprecedented (ethanol)4 cluster is observed in a photoluminescent silver(I) coordination polymer host, [Ag2(dmt)2(nda)·2EtOH]n (1, dmt = 2,4-diamino-6-methyl-1,3,5-triazine, H2nda = naphthalene-1,4-dicarboxylic acid, EtOH = ethanol). In 1, two pairs of symmetry-related ethanol molecules are hydrogen bonded with each other by O―H⋯O hydrogen bonds to form a R 4 4(8) hydrogen bond motif where all the ethanol molecules are proton acceptor and proton donor at the same time. The thermal stability and luminescent behavior of 1 were also discussed.A novel centrosymmetric (ethanol)4 cluster, encapsulated in a photoluminescent silver(I) coordination polymer host, was firstly observed and characterized.Display Omitted► One silver(I) coordination polymer was synthesized and characterized. ► A rare (ethanol)4 cluster is observed in this silver(I) coordination polymer. ► The structure of this complex was confirmed by X-ray crystallography.
Keywords: Silver(I); 2,4-Diamino-6-methyl-1,3,5-triazine; Naphthalene-1,4-dicarboxylic acid; Ethanol cluster; Crystal structure;

A new 3D sandwich-type MOF named [Zn3(bptc)1.5(H2O)4]·C2H5OH·2H2O (1) (H4bptc = biphenyl-2,5,2',5'-tetracarboxylic acid) was obtained by solvothermal reaction, which represents a rare trinodal (3, 4, 10)-connected topology network. Moreover, the thermal stability, UV–vis absorption spectra and photoluminescent properties of 1 have been investigated as well.A novel 3D zinc coordination complex was synthesized through solvothermal reaction between zinc salt and H4bptc. The complex 1 exhibits a rare (3, 4, 10)-connected topology network. In addition, the thermal stability, UV-vis absorption spectra and photoluminescent properties of 1 have been investigated.Display Omitted► New sandwich-type complex with trinuclear zinc(II) cluster and two kinds of discrete zinc(II) ions has been synthesized. ► Three-dimensional framework of [Zn3(bptc)1.5(H2O)4]·C2H5OH·2H2O exhibits a rare trinodal (3, 4, 10)-connected topology. ► The UV–vis absorption spectra and photoluminescent properties at room temperature has been investigated.
Keywords: Crystal structure; Biphenyl-2,5,2',5'-tetracarboxylic acid; Topology; Photoluminescent;

The synthesis and characterization of novel metal-free and cobalt phthalocyanine, peripherally symmetrically derived from 2,3,6,7,10,11,13,14-octahydro-5H,9H-4,12-(propanothiopropano)-1,8,15,23,4,12-benzotetrathiodiazacycloheptadecane-17,18-dicarbonitrile (4) which was prepared by the reaction of 1,9-diaza-5,13-dithiocyclohexadecane (3) and 1,2-bis(2-iodoethylmercapto)-4,5-dicyanobenzene (2) was carried out. The novel compounds were characterized by using elemental analysis, 1H, 13C NMR, IR, UV–vis and MS techniques.New metal-free phthalocyanine (H 2 Pc) and cobalt phthalocyanine (CoPc) containing four peripheral mixed donor macrobicyclic moieties has been prepared by a cyclotetramerisation reaction of macrobicyclic dinitrile (4).Display Omitted► Different synthetic approaches concerning (2) was investigated and the novel route was found. ► The synthesis of compound (4) containing N2S4 macrobicyclic moiety has been accomplished. ► Novel phthalocyanines bearing peripheral N2S4 macrobicyclic moieties were synthesized.
Keywords: Nitrogen-sulfur mixed donor; Macrobicycle; Phthalocyanine; Cobalt complex; High dilution;

A novel cationic dinuclear ruthenium complex [RuCl(HL)(TFTPP)]2 (H2L = 2,6-bis(5-phenyl-1H-pyrazol-3-yl)pyridine; TFTPP = tri(p-trifluoromethylphenyl)phosphine) has been synthesized and characterized by 31P{1H} NMR, 1H NMR, elemental analysis and X-ray crystallography. This complex is the first cationic dinuclear ruthenium complex bearing N4 ligand characterized by single crystal X-ray analysis. It exhibits good catalytic activity for the transfer hydrogenation of ketones in refluxing 2-propanol.A novel cationic dinuclear complex [Ru(HL)(TFTPP)Cl]2 (H2L = 2,6-bis(5-phenyl-1H-pyrazol-3-yl)pyridine; TFTPP = tri(p-trifluoromethylphenyl)phosphine) has been synthesized and it exhibited a good catalytic activity in the transfer hydrogenation of ketones.Display Omitted► A novel cationic dinuclear ruthenium complex bearing N4 ligand has been synthesized and characterized. ► Complex 1 is the first crystallographic determination of bimetallic Ru complex with N4 ligand. ► Complex 1 is an efficient catalyst in the transfer hydrogenation of ketones, even with 0.02 mol% loading.
Keywords: Ruthenium; N4 ligand; Dinuclear complex; Transfer hydrogenation; Ketone;

Structure and physical properties of Mn(II) and Co(II) complexes with multicarboxylate ligands by Qin Huang; Lihong Diao; Chuang Zhang; Fuhou Lei (1889-1893).
Three new metal-organic coordination polymers, [Mn(4,4′-bpy)(H2BTCA)(H2O)2](4,4′-bpy) (1), [Na2Co(BTCA)0.5(OXA)]·3H2O (2) and [Na2Co(BTCA)(H2O)2] (3), (H4BTCA = benzene-1,2,4,5-tetracarboxylic acid, H2OXA = oxalic acid) have been synthesized, which are characterized by elemental analysis, infrared spectrum and x-ray crystal diffraction. Complex 1 possesses a 3D polymeric structure, which is comprised of (4,4)-layers. Hydrogen bonds play a dominant role in the construction of the final 3D supramolecule. 1D channels are observed in complex 2, which can be ascribed to pillared-layer motifs.A novel Co(II) complex with 1,2,4,5-benzenetetracarboxylate ligand, which contain 1D open channel along c-axis direction.Display Omitted► Compound 1 is constructed from 2D (4,4) layers. ► Ellipse-like channels were observed along c-axis in complex 2. ► Complex 2 displays good gas sorption/desorption.
Keywords: Porous complex; 1,2,4,5-benzenetetracarboxylate; Gas adsorption; Pillar–layer;

Phosphorescent copper(I) complexes bearing 2-(2-benzimidazolyl)-6-methylpyridine and phosphine mixed ligands by Jing-Lin Chen; Xing-Fu Cao; Wei Gu; He-Rui Wen; Lin-Xi Shi; Gan Rong; Pan Luo (1894-1897).
Two 2-(2-benzimidazolyl)-6-methylpyridine (Hbmp) copper(I) complexes bearing PPh3 and 1,4-bis(diphenylphosphino)butane (dppb), namely, [Cu(Hbmp)(PPh3)2](ClO4) (1) and [Cu(Hbmp)(dppb)](ClO4) (2), have been synthesized. X-ray diffraction analysis reveals that the most significant influence of the phosphine ligands on the structures is on the P–Cu–P bond angle. Both two Cu(I) complexes exhibit a weak low-energy absorption at 360–450 nm, ascribed to the Cu(I) to Hbmp metal-to-ligand charge-transfer (MLCT) transition, perhaps mixed with some ILCT character inside Hbmp. The room-temperature luminescences are observed for 1 and 2, both in solution and in the solid state, which originate from the MLCT excited states and vary markedly with the phosphine ligands.Two phosphorescent copper(I) complexes of 2-(2-benzimidazolyl)-6-methylpyridine (Hbmp), [Cu(Hbmp)(PPh3)2](ClO4) (1) and [Cu(Hbmp)(dppb)](ClO4) (2), have been synthesized and characterized. It is demonstrated that the auxiliary phosphine ligands have a significant impact on both the P–Cu–P bond angles and the photophysical properties of Cu(I) complexes.Display Omitted▶ Two new phosphorescent Cu(I) complexes of 2-(2-benzimidazolyl)-6-methylpyridine. ▶ One notable impact of the phosphine ancillary ligand is on the P–Cu–P bond angle. ▶ The phosphine ligands have significant effects on the photophysical properties. ▶ The P–Cu–P bond angles also play an important role in the emissive properties.
Keywords: Copper(I); Mixed-ligand; Photoluminescence; 2-(2-Benzimidazolyl)-6-methylpyridine;

A new self-assembly gadolinium(III)–iron(II) complex (Gd2Fe) was synthesized and characterized. Relaxivity studies showed that complex Gd2Fe exhibited higher relaxation efficiency compared with the clinically used Gd-DTPA. In vitro MR images on a 0.5 T magnetic field exhibited a remarkable enhancement of signal contrast for Gd2Fe than Gd-DTPA. The results indicated that Gd2Fe could serve as a potential MRI contrast agent.A new heterotrinuclear gadolinium(III)–iron(II) complex (Gd2Fe) exhibits the T 1-relaxivities of 7.56 mM− 1·s− 1 in 50 mM HEPES buffer (pH = 7.2) solution and 8.66 mM− 1·s− 1 in 0.725 mM HSA solution, which could serve as a potential MRI contrast agent.Display Omitted► A self-assembly Gd(III)–Fe(II) complex (Gd2Fe) was synthesized and characterized. ► It exhibited higher relaxation efficiency than the clinically used Gd-DTPA. ► A remarkable enhancement of signal contrast was found in vitro MR images. ► Gd2Fe complex could serve as a potential MRI contrast agent.
Keywords: Gadolinium; Self-assembly; MRI; Relaxivity; Contrast agent;

The reaction of AgClO4·6H2O with (+/−)-trans-epoxysuccinic acid (H2 tes) in the presence of 2,6-dimethylpyridine afforded a three-dimensional (3-D) AgI coordination polymer [Ag2(tes)] (1), which exhibits an unusual 5-connected self-penetrating (44·66)2 topological net (tes  = (+/−)-trans-epoxysuccinate). Comparison of the structural differences with our relevant finding, a two-dimensional (2-D) (4,8)-connected (45·6)2(418·610) coordination polymer [Ag4(ces)2] (S1) (ces  =  cis-epoxysuccinate), suggests that the carboxyl configuration on the ternary ring backbone of H2 tes or H2 ces ligand plays an important role in the construction of coordination networks.► A unique 3-D AgI complex with the 5-connected self-penetrating (44·66)2 topology. ► Carboxyl configurations play an important role in coordination construction. ► Offering effective means for constructing unique coordination networks.A unique 3-D AgI coordination polymer [Ag2(tes)]∞ (tes=(+/−)-trans-epoxysuccinate), exhibiting an unusual 5-connected self-penetrating (44•66)2 topology, is presented. Comparison of the structural differences with our relevant finding suggests that the carboxyl configuration on the ternary ring backbone of ligands plays an important role in the construction of such coordination networks.Display Omitted
Keywords: Silver(I) complexes’; trans-/cis-Epoxysuccinate ligand; Carboxyl configuration; Crystal structure; Topology;

An unusual three-dimensional (3D) pillared-layer 3d–4f (Cu+–Sm3+) heterometallic coordination polymer, {Sm2Cu7Br6(IN)7(H2O)5·3H2O} n (1) (HIN = isonicotinic acid), has been successfully synthesized by hydrothermal reaction of Sm2O3, CuBr2, HIN, HClO4 and H2O, and characterized by elemental analyses, IR, PXRD, and single-crystal X-ray diffraction. The structure determination reveals that 1 possesses 3D heterometallic framework constructed upon unprecedented [Cu7Br6] n n+ inorganic layers linked by dimeric Sm2(IN)6 pillars. Additionally, the thermogravimetric analysis and luminescent property of 1 were investigated and discussed.The {Sm2Cu7Br6(IN)7(H2O)5·3H2O} n is the first example of 3D 3d–4f heterometallic coordination polymer based on 2D Cu–Br inorganic layers.Display Omitted► A novel 3D Sm–Cu coordination polymer based on 2D Cu-Br layers has been synthesized. ► CuBr2N triangles and CuBr3N tetrahedra construct the unprecedented 2D Cu-Br layer. ► This compound exhibits good luminescent property.
Keywords: 3d–4f heterometallic coordination polymer; Crystal structure; Luminescent property;

An open metal–organic framework based on Cu3-triad triangular units and templated by double Wells–Dawson anions by Dan-dan Wang; Jun Peng; Peng-peng Zhang; Xiang Wang; Min Zhu; Ming-guan Liu; Cui-li Meng; Kundawlet Alimaje (1911-1914).
A novel double-Dawson-anion-templated, triangular trinuclear Cu-trz unit-based metal–organic framework [CuII 8(trz)63-O)2(H2O)12][P2W18O62]·4H2O (1) (Htrz = 1,2,4-triazole), has been hydrothermally synthesized and characterized by routine methods. Compound 1 is the first example of the Cu3-triad triangular unit-based three-dimensional (3D) metal–organic framework templated by double [P2W18O62]6− polyoxoanions. Furthermore, the electrochemical property of compound 1 has been studied.A beautiful metal–organic framework with mango-like 1D channels is based on Cu3-triad triangular units and templated by double Wells–Dawson anions.Display Omitted► A beautiful 3D metal organic framework with mango-like 1D channels is constructed from Cu3-triad triangular unit. ► The first example of trinuclear triangular CuII-trz unit-based MOFs with Dawson-type polyoxoanions as a double-template. ► The electrochemical behavior is also studied.
Keywords: Polyoxometalate; Double templates; Cu3-triad triangular unit; Electrochemical property;

A new three-dimensional terbium-carboxylate framework [Tb4L3(H2O)9]·7H2O (1) [(H4L = 4,4′-(hexafluoroisopropylidene)diphthalic acid)] has been hydrothermally synthesized and structurally characterized. The framework contains Tb2 and Tb4 clusters, and exhibits an unprecedented 4-nodal (3,4,5,8)-connected topology. In addition, the thermogravimetric analysis, luminescent and magnetic properties were investigated.A new terbium metal-organic framework featuring an unprecedented 4-nodal (3,4,5,8)-connected topology has been constructed by the assembly of Tb2 and Tb4 clusters and 4,4′-(hexafluoroisopropylidene)diphthalate tetracarboxylate ligand, which exhibits both antiferromagnetic and strong luminescent properties.Display Omitted► A new terbium-carboxylate framework possessing Tb2 and Tb4 clusters. ► The framework displays an unprecedented 4-nodal (3,4,5,8)-connected net. ► The framework exhibits both antiferromagnetic and green luminescent properties.
Keywords: Metal-organic framework; Lanthanide; Topology; Luminescence;

This paper reports two alkaline-earth metal phosphonates with formulae M(4-cppH2)2 [M = Sr (1), Ba (2); 4-cppH3  = 4-carboxylphenylphosphonic acid]. Compound 1 shows a chain structure made up of edge-sharing {SrO8} polyhedra and {PO3C} tetrahedra. While in compound 2, the edge-sharing {BaO8} polyhedra are connected by the {PO3C} tetrahedra to form a two-dimensional inorganic layer. Neighboring chains in 1 or layers in 2 are cross-linked by hydrogen bond interactions between the protonated carboxylate groups, resulting in three-dimensional supramolecular structures. The magnesium alloys coated with 1 or 2 films show significantly improved anti-corrosion behaviors compared to the bare substrate.The alkaline-earth metal phosphonates Sr(4-cppH2)2 (1) with a chain structure and Ba(4-cppH2)2 (2) with a layer structure are reported based on 4-carboxylphenylphosphonic acid. The magnesium alloy coated by 1 or 2 films shows significantly improved anti-corrosion behaviors.Display Omitted► Alkaline-earth metal phosphonates with chain and layer structures showing anti-corrosion behaviors on magnesium alloy surface. ► Strontium and barium 4-carboxylphenylphosphonates as corrosion inhibitors on magnesium alloy surface. ► Hybrid alkaline-earth metal phosphonate polymers as corrosion inhibitor on magnesium alloy surface.
Keywords: Strontium; Barium; 4-Carboxylphenylphosphonic acid; Crystal structure; Anti-corrosion behavior;

A novel 3D inorganic–organic hybrid compound {[Cu3(en)(TTHA)(H2O)4]·4.25H2O}n(1) (TTHA = 1,3,5-triazine-2,4,6-triamine hexaacetic acid; en = ethylenediamine) has been synthesized and characterized. Topological analysis shows that the compound is a new 3,10-connected 2-nodal net with point symbol (418.624.83)(43)2, further simplification of the structure by merging two 3-connected nodes and one 10-connected node together gives a rare uninodal 8-connected hex net, we conclude that the 2-nodal net found in the network is a hex-originated supernet. TG, IR, PXRD and photoluminescent spectra of the compound 1 are investigated.3,10-connected 2-nodal net with point symbol (418.624.83)(43)2 is a supernet of hex originated.Display Omitted► Topological analysis shows that the compound is a new 3,10-connected 2-nodal net. ► Simplification of the structure by merging together two 3-connected nodes and one 10-connected node gives a rare hex net. ► The 2-nodal net found in the network is a supernet of hex originated.
Keywords: Inorganic–organic hybrid compound; TTHA; Topological analysis; Hex net;

Under hydrothermal conditions, Sm(NO3)3·6H2O reacts with N-(2-Hydroxyethyl)iminodiacetic acid (H3heidi), oxalic acid (H2Ox), in the presence of NiCl2·6H2O and NaOH, producing a novel two dimensional coordination polymer with the empirical formula of Na[Sm(Hheidi)(Ox)]·2H2O (1). X-ray diffraction analyses show that 1 crystallizes in the orthorhombic system, Pna21 space group, a  = 25.9008(19) Å, b  = 6.2593(5) Å, c  = 8.7624(6) Å, in which the network of SmNO8 and oxalate units forms an extended two dimensional layered structure. To the best of our knowledge, 1 represents the first structurally characterized lanthanide complex containing H3heidi ligand. The variable-temperature magnetic property of 1 has been investigated and the results of magnetic determination suggest the existence of a weak antiferromagnetic coupling between the samarium ions.We describe the syntheses and magnetic properties of a novel 2D samarium complex, in which the SmIII adopts a nine-coordinate distorted monocapped square anti-prism geometry defined by an NO8 donor set from two N-(2-Hydroxyethyl)iminodiacetic acid and two oxalate acid ligands. Magnetic determination suggests the existence of a weak antiferromagnetic coupling.Display Omitted► The syntheses and magnetism properties of a novel 2D samarium complex is described. ► 1 is the first lanthanide complex containing H3heidi li-gand. ► Magnetic determination suggest the existence of a weak antiferromagnetic coupling.
Keywords: H3heidi; Samarium(III) complex; Crystal structure; Magnetic property;

Illusive tungsten-imido-dithiocarbamate complexes: Facile carbon–nitrogen bond formation by Alexander Edwards; Graeme Hogarth; Nathan Hollingsworth; Joseph J. Oller (1932-1936).
Heating [WO2(S2CNBui 2)2] with a slight excess of ArNCO (Ar = Ph, p-tolyl) results in the rapid formation of imido-ureato complexes [W(NAr){κ2-ArNC(O)NAr}(S2CNBui 2)2], a transformation believed to occur via the bis(imido) intermediates [W(NAr)2(S2CNBui 2)2]. The ureato ligand is easily removed (as the urea) upon addition of gaseous HCl to afford the dichloride [W(NAr)Cl2(S2CNBui 2)2]. While bis(imido) complexes are unavailable from the direct reaction of isocyanates (or amines) with [WO2(S2CNBui 2)2], they can be prepared upon addition of dithiocarbamate salts to [W(NBut)2(NHBut)2] addition of two equivalents of [NH2Bui 2][Bui 2NCS2] affording [W(NBut)2(S2CNBui 2)2] in which both imido groups are linear.Heating [WO2(S2CNBui 2)2] with three equivalents of ArNCO (Ar = Ph, p-tolyl) results in the rapid formation of imido-ureato complexes [W(NAr){κ2-ArNC(O)NAr}(S2CNBui 2)2], a transformation believed to occur via the bis(imido) intermediates [W(NAr)2(S2CNBui 2)2], an example of which, [W(NBut)2(S2CNBui 2)2], is prepared upon addition of dithiocarbamate salt to [W(NBut)2(NHBut)2].Display Omitted► Tungsten-imido-dithiocarbamate complexes are reported for the first time. ► Two different routes have been developed from tungsten oxo and tungsten imido precursors. ► The imido ligands appear to be quite reactive and undergo cycloaddition with organic isocyanates.
Keywords: Tungsten; Imido; Dithiocarbamate; Oxo; Ureato;

A thiocyanate-bridging dimeric cyclometalated iridium(III) complex: Synthesis, structure and phosphorescence behaviours towards metal ions by Bihai Tong; Jia-Yan Qiang; Ya-Qing Xu; Qunbo Mei; Taike Duan; Qun Chen; Qian-Feng Zhang (1937-1939).
A new neutral dimeric cyclometalated iridium complex containing bridging thiocyanate ligands, [{Ir(μ-SCN)(pqcm)2}2] (1, pqcmH = 2-phenyl-quinoline-4- carboxylic acid methyl ester), has been synthesized and structurally characterized. The photoluminescence (PL) spectrum of 1 shows emission maximum at 638 nm with a lifetime of 0.11 μs and the PL quantum yield is ca. 0.012. The phosphorescence behaviours of 1 towards different solvents and metal ions were also investigated and the strong phosphorescence quenching by acetonitrile and two equivalents of Hg2+, Cu2+ and Ag+ ions were observed.A neutral dimeric cyclometalated iridium complex containing bridging thiocyanate ligands has been synthesized and structurally characterized, and show a short lifetime of 0.11 μs and the quenching of phosphorescence in the presence of acetonitrile or two equivalents of Hg2+, Cu2+ and Ag+ ions.Display Omitted► Luminescent cyclometalated iridium(III) complexes. ► Cyclometalated iridium(III) thiocyanate-bridging dimer. ► Short lifetime and the quenching of phosphorescence. ► Phosphorescence behaviours towards metal ions.
Keywords: Cyclometalated iridium(III); Dimeric complex; Crystal structure; Photoluminescence; Phosphorescence;

A new eight-connected CsCl-type topological net based on trinuclear Co(II) clusters as nodes by Yien Du; Xiao-Fang Wang; Yan-Fang Liang; Jian-Wei Ji; Zheng-Bo Han (1940-1943).
Ionothermal reaction of isophthalate (H2ip), and colbolt(II) nitrate under 1-ethly-3-methylimidazolium bromide (EMimBr) as solvent leads to a novel three dimensional metal–organic framework (EMim)2[Co3(ip)4] (1). It can be described as an eight-connected CsCl-type net (42464) utilizing trinuclear Co(II) clusters as eight-connected nodes and ip ligands as linkers. The imidazolium cation [EMim]+ of the ionic liquid acting as charge-compensating agents has interactions with the framework. The magnetic properties studies show ferrimagnetic behavior for 1.Ionothermal reaction of isophthalate and Co(II) leads to the generation of a three dimensional complex, (EMim)2[Co3(ip)4]. It can be described as a eight-connected CsCl-type net based on trinuclear Co(II) clusters as eight-connected nodes and ip ligands as linkers. The magnetic properties studies show ferrimagnetic behavior.Display Omitted► A 3D complex (EMim)2[Co3(ip)]4 has beeen synthesized under ionothermal conditions. ► It can be described as a CsCl-type net based on trinuclear Co(II) clusters as nodes. ► The imidazolium cation has strong interaction with the framework.
Keywords: Ionothermal synthesis; Ionic liquid; Metal–organic framework; Trinuclear building unit;

Rhenium(I) tricarbonyl complexes based on the new tetrathiafulvalene bipyridine ligand by Tao Jin; Gao-Nan Li; Xin-Hui Zhou; Jing-Lin Zuo (1944-1947).
Using the deprotection–realkylation methodology, a new electroactive tetrathiafulvalene-based bipyridine ligand, 5-[{2-[4,5-Bis(methylthio)-1,3-dithiol-2-ylidene]-5-(methylthio)-1,3-dithiol-4-yl}thio]-methyl-2,2′-bipyridine (L), has been synthesized. Reactions of the above ligand with Re(CO)5Br or Re(CO)5Cl afford the corresponding tricarbonyl rhenium(I) complexes ReL(CO)3X (X = Br, 1; X = Cl, 2), respectively. Crystal structures of 1 and 2 have been described. The absorption properties of these new compounds have been studied. Electrochemical measurements have been performed and TTF/TTF+•/TTF2+ redox processes are observed.Two rhenium(I) tricarbonyl complexes with the new electroactive tetrathiafulvalene-based bipyridine ligand, 5-[{2-[4,5-Bis(methylthio)-1,3-dithiol-2-ylidene]-5-(methylthio)-1,3-dithiol-4-yl}thio]-methyl-2,2′-bipyridine (L), have been prepared and structurally characterized. The absorption and electrochemical properties of these new compounds have been studied.Display Omitted► A new electroactive tetrathiafulvalene-based bipyridine ligand is synthesized. ► Two rhenium(I) tricarbonyl complexes based on the ligand are structurally characterized. ► The TTF/TTF+•/TTF2+ redox processes are observed for the ligand and the related metal complexes.
Keywords: Tetrathiafulvalenes; Crystal structures; Bipyridine ligands; Rhenium complexes;

Three carbon-bridged bis(phenolate) neodymium complexes, [(MBMP)2Nd(μ3–Cl)Li(THF)2Li(THF)] (1), [(MBBP)2Nd(μ3-Cl)Li(THF)2Li(THF)] (2) and [(THF)2Nd(EDBP)2Li(THF)] (3) have been synthesized by one-pot reaction of NdCl3 and LiCH2SiMe3 with 6,6′-methylenebis(2-tert-butyl-4-methylphenol) (MBMP-H2), 6,6′-methylenebis(2,4-di-tert-butylphenol) (MBBP-H2) or 6,6′-(ethane- 1,1-diyl)bis(2,4-di-tert-butylphenol) (EDBP-H2), respectively, in a molar ratio of 1:4:2. The definitive structures of complexes 2 and 3 were determined by X-ray diffraction studies. Experimental results show that 13 efficiently initiate the ring-opening polymerization (ROP) of ε-caprolactone and ROP of L-lactide.Three carbon-bridged bis(phenolate) neodymium complexes were synthesized and two of them were characterized by X-ray diffraction analysis. They are efficient initiators for the polymerization of ε-caprolactone and polymerization of L-lactide.Display Omitted► Synthesis and characterization of 3 carbon-bridged bis(phenolate) neodymium complexes. ► X-ray diffraction studies on 2 of these complexes. ► These complexes are efficient initiators for the ring-opening polymerization of ε-caprolactone as well as L-lactide.
Keywords: Neodymium complexes; Ligands; Catalysts; Polymerization; Cyclic esters;

A 3D metal-organic framework {[Cd2(TZ)3(BDC)0.5]·5H2O} n (1·5nH2O) (HTZ = 1H-tetrazole, H2BDC = 1,4-benzenedicarboxylic acid), has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. The phase purity was confirmed by powder X-ray diffraction (PXRD), and the stability was identified by thermal gravimetric analysis (TG) and variable-temperature powder X-ray diffraction (VT-PXRD). The result of the single-crystal X-ray diffraction analysis indicates that 1 is a novel 3D microporous metal-organic framework constructed from Cd(II) metal centers and mixed linkers of TZ anions and BDC2− anions. Photoluminescent measurement elucidates that 1 displays a strong and broad emission peak at 423 nm, which suggests that 1 may be a potential purple-light material.A 3D metal-organic framework {[Cd2(TZ)3(BDC)0.5]·5H2O} n (1·5nH2O) (HTZ = 1H-tetrazole, H2BDC = 1,4-benzenedicarboxylic acid), has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. The phase purity was confirmed by powder X-ray diffraction (PXRD), and the stability was identified by thermal gravimetric analysis (TG) and variable temperature powder X-ray diffraction (VT-PXRD). Photoluminescent measurement elucidates that 1 shows good luminescent property.Display Omitted► A novel 3D metal-organic framework (MOF) based on mixed ligands was synthesized. ► The good thermal stability of this MOF was characterized by TG and VT-PXRD. ► This MOF may be a potential purple-light material.
Keywords: 1H-tetrazole; 1,4-benzenedicarboxylic acid; Metal-organic framework; Coordination polymer; Luminescence;

Crystal structures and optical properties of 1-D iodoplumbates templated by in situ synthesized p-phenylenediamine derivatives by Guan-E Wang; Ming-Sheng Wang; Xiao-Ming Jiang; Zhi-Fa Liu; Rong-Guang Lin; Li-Zhen Cai; Guo-Cong Guo; Jin-Shun Huang (1957-1961).
Two inorganic–organic hybrids, (MPDA)2n (Pb3I10) n (MPDA =  p-Me3NC6H4NMe3) (1) and (H2EPDA) n (Pb2I6) n ·2nH2O (H2EPDA =  p-Et2NHC6H4NHEt2) (2), have been solvothermally synthesized using p-phenylenediamine (PDA) as a precursor. Their iodoplumbate ions all show 1-D chain structures, but differ in interlinkage modes of [PbI6] octahedra: the former is both face- and edge-sharing, while the latter is face-sharing. The chain-like structure in 1 was reported only once in the literature. The results of optical absorption spectra and theoretical calculations for compounds PbI2 and 12 reveal a quantum confinement effect. Photoluminescent analyses show that they all exhibit blue emissions upon UV irradiation, which mainly originate from charge transfer from iodine atoms to ammoniums.The interlinkage modes of (PbI6) octahedra in 1-D iodoplumbate anions have been found to develop from edge- to face-sharing along with the increase of steric hindrance and the decrease of the charge density of p-phenylenediamine (PDA) derivatives. Photoluminescence (PL) studies suggest that bulk PbI2 is PL silent but introducing the N-alkylated derivatives of PDA to it can result in the generation of PL emission, which mainly originate from the charge transfer from I atoms to ammoniums.Display Omitted► Study the effect of modification of the same organic ammonium on crystal structure. ► One of the 1-D chain structure of the iodoplumbates was rarely reported. ► Study the influence of templates on absorption edge and photoluminescence emission.
Keywords: Inorganic–organic hybrid; Interlinkage modes; Iodoplumbates; Photoluminescence; Semiconducting;

Synthesis, crystal structure and antimicrobial studies of chlorido(dimethylsulfoxide-κS)(pyrrolidinedithiocarbamato-κ 2 S,S/)platinum(II) by Anvarhusein A. Isab; Muhammad Akhtar Javed Ali; Shahzad Sharif; Islam Ullah Khan; Sung Kwon Kang; Tanzeel Khalid; Muhammad Saleem; Saeed Ahmad (1962-1965).
Platinum(II) complexes, [Pt(PDTC)(H2O)Cl] and [Pt(PDTC)(DMSO)Cl] (1) (PDTC = pyrrolidinedithiocarbamate) have been prepared and characterized by IR, NMR and X-ray crystallographic methods. In the crystal structure of 1 the central platinum atom is coordinated to two sulfur atoms of PDTC, one sulfur atom of DMSO and one chloride ion adopting a square planar geometry with the average cis and trans bond angles of 90.00° and 171.62° respectively. The 1H and 13C NMR spectral data indicate the coordination of both PDTC and DMSO to platinum(II). The title complex was screened for antimicrobial effects and the results show that it exhibits significant activity against gram-negative bacteria (E. coli, P. aeruginosa), while the activities are moderate against molds (A. niger, P. citrinum) and yeasts (C. albicans, S. serevisaiae).Platinum(II) complexes, [Pt(PDTC)(H2O)Cl] and [Pt(PDTC)(DMSO)Cl] (1) (PDTC = pyrrolidinedithiocarbamate) have been prepared and characterized by IR, NMR and X-ray crystallographic methods. In the crystal structure of 1 the platinum atom is coordinated to two sulfur atoms of PDTC, one sulfur atom of DMSO and to one chloride ion adopting a square planar geometry. The complex 1 exhibits significant activity against gram-negative bacteria (E. coli, P. aeruginosa), while the activities are moderate against molds and yeasts.Display Omitted► The synthesis and structural characterization of a novel Platinum(II) complex of pyrrolidinedithiocarbamate and DMSO. ► Investigation of antimicrobial activities. ► The significant antibacterial activities of the complex may lead to the development of new antimicrobial agents.
Keywords: Platinum(II) complexes; Pyrrolidinedithiocarbamate; X-ray structure; Antimicrobial activity;

A new stable mixed-ligand metal organic framework Zn2(tpt)2(2-atp)I2 1 (tpt = tris (4-pyridyl) triazine, 2-atp = 2-aminoterephthalate) with split channels has been synthesized and characterized. The nitrogen containing ligands tpt and 2-atp are selected to create attractive basic sites for the catalyst. The Knoevenagel condensation between benzaldehyde and the active hydrogen compound (ethyl cyanoacetate or malononitrile) is carried out using compound 1 as solid basic catalytic support. The test results indicate that 1 is an efficient base catalyst with selective catalytic properties. It gives 37% and 99% yield respectively for the condensation products ethyl (E)-α-cyanocinnamate and 2-benzylidenemalononitrile. TG data show that the solid catalyst sample is fairly thermally stable. The compound does not show any signs of decomposition until 420 °C. PXRD data support that the catalyst remains its crystalline and framework stability after the catalysis process. These characters make it easily to be regenerated for the next cycle.A new stable mixed-ligand metal organic framework Zn2(tpt)2(2-atp)I2 1 with split channels has been synthesized and characterized. It is an efficient catalyst with selective base catalytic properties. The robust framework makes it easily to be regenerated for the next cycle.Display Omitted► A new stable MOF with split channels has been synthesized and characterized. ► The structure is characterized by single crystal data. ► Purity and stability of the bulk sample are confirmed by TG and XRPD data. ► It is tested as solid catalytic support in the knoevenagel condensation. ► The efficient base catalyst has an interesting size selectivity character.
Keywords: Metal organic framework; Structure and characterization; Solid base, Knoevenagel condensation; Heterogeneous catalysis;

A heteroleptic nickel-bis-1,2-dithiolene ion–pair complex, [BzQl][Ni(dmit)(mnt)] (where BzQl+  = 1-(benzyl)quinolinium; dmit2−  = 2-thioxo-1,3-dithiole-4,5-dithiolate, mnt2−  = maleonitriledithiolate), was synthesized and characterized structurally, which exhibited novel magnetic bistability. The compound crystallized in triclinic system with space group P-1. The anions and cations form alternating layered alignments, and the anionic layer is built by the irregularly heteroleptic [Ni(dmit)(mnt)] chains, where the neighboring anions are connected via lateral-to-lateral S…S contacts of dmit2− ligands. The temperature dependences of magnetic susceptibility follow the S = ½ Heisenberg alternating linear-chain model in high-temperature phase and Curie–Weiss law in low-temperature phase.A heteroleptic nickel-bis-1,2-dithiolene compound contains a one-dimensional S = ½ magnetic chain and exhibits an unusual hysteretic magnetic transition behavior.Display Omitted► A heteroleptic nickel-bis-1,2-dithiolene complex as magnetic molecular architecture. ► New one-dimensional irregular S = ½ magnetic chain. ► Double maximums of magnetic susceptibility. ► Hysteretic magnetic transition.
Keywords: Heteroleptic metal–dithiolene complex; Alternating linear spin chain; Magnetic bistability;

A new manganese(II) terephthalate layer with 6-connected hxl topology and antiferromagnetic property by Zhi-Qiang Jiang; Zhen Zhao; Gui-Yuan Jiang; Duan-Chuan Hou; Yao Kang (1975-1977).
A novel two-dimensional (2D) Mn(II) coordination polymer [Mn1.5(H2bdc)1.5(DMA)2] (1; H2bdc = terephthalic acid; DMA = N,N′-dimethylacetamide) based on trinuclear manganese subunit has been solvothermally prepared and structurally characterized by single-crystal X-ray diffraction. Compound 1 exhibits a rare layered structure with 6-connected hxl topology constructed from the trinuclear Mn3(COO)6 units, and further stacking of layers leads to a 3D supramolecular framework. The thermalgravimetric behavior and magnetic property of 1 have been also investigated. The magnetic susceptibility measurements reveal that the compound exhibits antiferromagnetic coupling interactions.Presented here is a novel two-dimensional (2D) Mn(II) coordination polymer constructed from trinuclear manganese subunits, which exhibits a rare layered structure with hxl topology and antiferromagnetic property.Display Omitted► A novel two-dimensional (2D) Mn(II) coordination polymer constructed from trinuclear manganese subunits. ► A rare layered structure with 6-connected hxl topology. ► Antiferromagnetic coupling interactions between Mn centers in the trinuclear Mn unit.
Keywords: Manganese; Solvothermal synthesis; Coordination polymer; Magnetic property;

A new salicylaldehyde derivative 1, i.e. 5-chloro-3-(ethoxymethyl)-2-hydroxybenzaldehyde, has been prepared and structurally characterized. A novel dinuclear copper(II) complex of its air-oxidized product 2 has been successfully yielded from the in situ copper(II) ion catalysis and complexation. Additionally, another control experiment has been carried out by using 3,5-dibromo-2-hydroxybenzaldehyde as the starting material, and a similar mononuclear air oxidation copper(II) complex 3 is obtained, where 3,5-dibromo-2-hydroxybenzaldehyde has also been in situ transformed to the divalent anion of 3,5-dibromo-2-hydroxybenzoic acid.Air oxidation of salicylaldehyde derivatives to corresponding acids is investigated under a mild experimental condition, in which salicylaldehyde derivatives are in situ catalyzed by a [Cu(bpy)(NO3)2] (bpy = 2,2′-bipyridine) complex and mononuclear and dinuclear copper(II) complexes 2 and 3 of air-oxidized divalent anionic carboxylates are successfully isolated and structurally characterized.Display Omitted► Air oxidation of salicylaldehyde to acid is investigated under a mild condition. ► Salicylaldehyde derivatives are in situ catalyzed by a [Cu(bpy)(NO3)2] complex. ► Mono- and dinuclear CuII complexes 2 and 3 are isolated and structurally characterized.
Keywords: Copper(II) complexes; In situ copper (II) ion catalysis; Air oxidation; Salicylaldehyde derivatives;

Synthesis, structure and characterizations of a novel 3D coordination polymer constructed from rare castellated inorganic chains by Quan-Guo Zhai; Cui-Cui Zhang; Shu-Ni Li; Yu-Cheng Jiang; Man-Cheng Hu (1982-1985).
Self-assembly of CdCl2 and 1,2,4-triazole under hydrothermal condition yields a novel three-dimensional coordination polymer, namely {[Cd8Cl4(Trz)12(H2O)]·2H2O} n (1) (Trz = 1,2,4-triazole). Single-crystal X-ray diffraction reveals that four of the five independent Cd centers are linked by two μ2-Cl and two μ3-Cl atoms to form novel heptanuclear [Cd7Cl4] clusters, which are connected by the bridging water molecules to generate an unprecedented 1D castellated inorganic chain. Furthermore, the fifth unique Cd center and the castellated Cd–Cl–O chain are joint to each other via six different μ3-Trz ligands to give a 3D organic–inorganic hybrid framework of 1.A novel 3D hybrid coordination polymer was obtained via the self-assembly of CdCl2 and 1,2,4-triazole under hydrothermal condition, which is constructed from unprecedented 1D castellated Cd–Cl–O inorganic chains and μ3-triazole ligands.Display Omitted► 1D castellated inorganic chain based on heptanuclear [Cd7Cl4] clusters. ► 3D organic–inorganic hybrid framework with rod-packing topology. ► Strong blue photoluminescence attributed to LMCT.
Keywords: 1,2,4-Triazole; Cadmium; Castellated chain; Coordination polymer;