Inorganic Chemistry Communications (v.14, #9)

Contents List (iii-xviii).

Synthesis and properties of a meso-tetraphenylporphyrin and its Zn (II) complex with a dicyanoisophorone borne by double bond in the β pyrrolic position by Wei-zai Ke; Liang Wang; Bin Song; Jia-xiang Yang; Yu-peng Tian; Yu-he Kan; Xu-tang Tao; Min-hua Jiang (1311-1313).
A novel porphyrin compound (W1) with D-π-A structure and its Zn (II) complex (Zn-W1) have been synthesized. W1 and Zn-W1 show a similar absorption and emission spectra of porphyrins. Their optical properties can be modulated by the substituent in the β pyrrolic position. W1 and Zn-W1 have preferable thermal stability, as indicated from TGA data. And Zn-W1 shows reversible redox wave in its dichloromethane solution. Also, DFT calculations were used to study these two compounds.A novel D-π-A structure with tetraphenylporphyrin as electron donor and dicyanoisophorone as electron acceptor was synthesized, and its Zn (II) complex was also prepared. And their optical and electrochemical properties and thermal stability were studied.Display Omitted► Planar polycrystalline LaCoO3 films have been evaluated on the complete oxidation of CO and ethanol ► The participation of the bulk of the film in the catalytic reaction is indicated by the thickness-independence of the weight-normalized rates. ► Thin-film based catalysts show high performance relative to conventional powder samples and can be used as potential of model catalysts for the systematic investigation of oxidation reactions.
Keywords: Porphyrin; Dicyanoisophorone; Metalloporphyrin; Photophysics;

A zigzag chain structural compound named Ni0.5{[Ni(en)]2[Ni(en)(H2O)]2[H3NiMo6W6O40]}·3H2O 1 (en = ethylenediamine) was hydrothermally synthesized and characterized by IR, TG and X-ray diffraction analysis. Structural analysis indicates that compound 1 exhibits an unusual Mo/W mixed NiII centered Keggin structure, which is tetra-capped by two [Ni(en)]2+ and two [Ni(en)(H2O)]2+ units. Two linkages of M–O–Ni(2) and M–O–Ni(4) connect two adjacent tetra-capping clusters in different directions, and it represents a novel inorganic–organic zigzag chain built on the NiII centered Keggin species. Compound 1 is demonstrated to be a high selectivity for benzaldehyde in the oxidation of styrene, while the magnetic data of complex 1 were fitted to the Curie–Weiss law and show antiferromagnetic interactions.A zigzag chain structural cluster compound, Ni0.5{[Ni(en)]2[Ni(en)(H2O)]2[H3NiMo6W6O40]}·3H2O 1 based on the novel Keggin derivative, exhibits an unusual Mo/W mixed NiII centered Keggin structure, which is tetra-capped by two [Ni(en)]2+ and two [Ni(en)(H2O)]2+ units. Two linkages of Mo(1)–O–Ni(2) and Mo(2)–O–Ni(4) connect the adjacent tetra-capping clusters in different directions, and it represents a novel inorganic–organic zigzag chain built on the NiII centered Keggin species.Display Omitted► A zigzag chain structural cluster compound, Ni0.5{[Ni(en)]2[Ni(en)(H2O)]2[H3NiMo6W6O40]}·3H2O 1 has been synthesized. ► Compound 1 exhibits an unusual Mo/W mixed NiII centered Keggin structure. ► Compound 1 shows high selectivity for benzaldehyde ca. 94.0%.
Keywords: M–O cluster; Tetra-capped; Keggin; Hydrothermal synthesis;

Copper(I) hydrazone complexes: Synthesis, structure, DNA binding, radical scavenging and computational studies by P. Krishnamoorthy; P. Sathyadevi; K. Senthilkumar; P. Thomas Muthiah; R. Ramesh; N. Dharmaraj (1318-1322).
Potential bidentate hydrazone ligands, HL1 (1) and HL2 (2) prepared by the condensation of benzaldehyde or furfuraldehyde with benzhydrazide upon reaction with [CuCl2(PPh3)2] yielded corresponding mononuclear complexes of the compositions [Cu(L1)(PPh3)2] (3) and [Cu(L2)(PPh3)2] (4). The exact nature of coordination of the hydrazones to the metal ion and the structure of the complexes were confirmed by spectral and single crystal X-ray diffraction studies. Interestingly, the reactions of 1 and 2 with [CuCl2(PPh3)2] resulted in the formation of the first structurally characterized copper(I) hydrazone complexes 3 and 4 along with the previously reported complex [CuCl(PPh3)3] 5 as a minor product in both the reactions. The metal complexes 3 and 4 showed significant binding towards calf thymus DNA (CT-DNA) via groove binding mode with binding constants in the magnitude 104–105  M− 1. In addition, the antioxidant activities of the complexes were also investigated through scavenging effect on DPPH•, NO˙ and OH˙ radicals. The density functional theory calculations of complex 4 also supported the structure and stability of the reduced complex.The new complexes of [Cu(L1)(PPh3)2] (3) and [Cu(L2)(PPh3)2] (4) were synthesized, characterized and their theoretical and biological studies were carried out.Display Omitted► Synthesis of new copper(I) hydrazone complexes. ► Structural characterization involving single crystal XRD. ► DNA binding, antioxidant and DFT studies were carried out.
Keywords: Copper(I) hydrazones; DNA binding; DFT studies;

Two novel coordination polymers based on 1,2,3,4-butanetetracarboxylic acid: Synthesis, structure, and luminescence properties by Xiang-Hao Han; Ming-Feng Li; Da-Lu Wang; Xiao Song; Bing Jiang; Ya-Guang Sun (1323-1328).
Two novel coordination polymers [Cd(BTC)1/2(H2O)3]·H2O (1) and [SmCu2K(BTC)2(H2O)4]·2H2O (2) (H4BTC = 1,2,3,4-butanetetracarboxylic acid) have been synthesized at room temperature. Single-crystal X-ray diffraction analysis has revealed that 1 forms a two-dimensional network, while 2 forms a heterometallic three-dimensional framework. Furthermore, the luminescence properties of 2 have been studied.Two novel coordination polymers [Cd(BTC)1/2(H2O)3]·H2O (1) and [SmCu2K(BTC)2(H2O)4]·2H2O (2) (H4BTC = 1,2,3,4-butanetetracarboxylic acid) have been synthesized at room temperature. Single-crystal X-ray diffraction analysis has revealed that 1 forms a two-dimensional network, while 2 forms a heterometallic three-dimensional framework. Furthermore, the luminescence properties of 2 have been studied.Display Omitted► We synthesized out [Cd(BTCA)1/2(H2O)3]·H2O (1) and [SmCu2K(BTCA)2(H2O)4]·2H2O (2). ► 2 is the first heterometallic H4BTCA complex including three types of metal atoms. ► We found the interesting butterfly-shaped secondary building unit(SBU) existed in 2.
Keywords: Flexible ligand; Heterometallic complex; Crystal structure; Luminescence;

A novel tetranuclear mixed-valence manganese(II/III) cluster [Mn4(hmp)6(N3)4] (1) where hmp is the anion of 2-hydroxymethylpyridine, was obtained by the reaction of manganese perchlorate with hmpH and NaN3 in acetonitrile. Complex 1 was characterized by chemical analysis, IR spectroscopy, single crystal X-ray diffraction and variable-temperature magnetic susceptibility studies. Complex 1 crystallizes in triclinic system with space group Pī consisting of mixed-valence Mn ions whose coordination geometry can be described as distorted octahedron. The magnetic properties were studied in the temperature range of 1.9–300 K and the results show that mixed-valence Mn ions are ferromagnetically coupled in the cluster leading to an S  = 9 ground state.A mixed-valence manganese(II/III) cluster [Mn4(hmp)6(N3)4] (hmp is the anion of 2-hydroxymethylpyridine) (1) was synthesized by reaction of manganese perchlorate with hmpH and NaN3 in acetonitrile. Single crystal X-ray diffraction showed each Mn ion owns a distorted octahedral coordination geometry. The magnetic studies indicate that Mn ions are ferromagnetically coupled in the cluster leading to an S  = 9 ground state.Display Omitted► A mixed-valence Mn4 cluster [Mn4(hmp)6(N3)4] (1) has been synthesized. ► Single crystal X-ray diffraction showed each Mn ion owns a distorted octahedral coordination geometry. ► The magnetic studies indicated that Mn ions are ferromagnetically coupled. ► Complex 1 can be employed as a building block forming extended metal complexes.
Keywords: Manganese cluster; Mixed-valence; 2-hydroxymethylpyridine; Crystal structure; Magnetism;

Distinct Cd(II)-tetrazole frameworks determined by auxiliary anions by Pengbin Pan; Chuan-Fu Sun; Shu-Mei Chen; Yuangen Yao (1333-1336).
Two new Cd(II)-tetrazole coordination polymers with different auxiliary anions, namely [Cd10(ATZ)13(ac)2(H2O)2F5]•2H2O (1) and [Cd3(ATZ)4Cl2(C2H5OH)2] (2), were solvothermally synthesized and structurally characterized. Both compounds exhibit interesting three-dimensional Cd-ATZ frameworks, but their coordination networks are totally different and show distinct topologies.Two new Cd-ATZ frameworks with different auxiliary anions exhibit distinct 12-nodal (3,4,5)-connected topology and 3-nodal (3,4)-connected topology, respectively.Display Omitted► New Cd(II)-tetrazole coordination polymers with different auxiliary anions. ► Three-dimensional Cd-ATZ frameworks with distinct topologies. ► Anion-controlled versatility of coordination frameworks.
Keywords: Solvothermal synthesis; Cadmiun; Coordination polymer; Structure;

A unique heteronuclear Schiff base compound, [(NiL)Na(NiL)]ClO4 (1), derived from the compartmental Schiff base ligand N,N′-(1,2-Phenylene)-bis(3-methoxysalicylideneimine) (H2L) has been prepared and its molecular structure has been elucidated on the basis of X-ray crystallography. The compound contains an octa-coordinated Na+ in trigonal dodecahedral geometry and two terminal square planar Ni(II).A unique heteronuclear Schiff base compound, [(NiL)Na(NiL)]ClO4 with two terminal square planar Ni(II) and trigonal dodecahedral Na+, derived from the Schiff base compartmental ligand N,N′-(1,2-Phenylene)-bis(3-methoxysalicylideneimine) (H2L) has been prepared and its molecular structure has been elucidated on the basis of by X-ray crystallography.Display Omitted► Unique heteronuclear Schiff base compound with a compartmental Schiff base ligand. ► Structure elucidated on the basis of X-ray crystallography. ► Octa-coordinated Na+ in trigonal dodecahedral geometry. ► Square planar Ni(II).
Keywords: Nickel(II); Sodium; Compartmental Schiff base; Crystal structure;

A new heptanuclear compound [{Cu(DPA)(H2O)CN}4{Cu(DPA)CN}2Fe][PF6]8·4H2O (1) (DPA = bis(pyridin-2-ylmethyl)amine ) was synthesized by the reaction of [Cu(DPA)]2+ unit and K3Fe(CN)6. The cyanometalate core is encapsulated by mononuclear copper moieties via each cyanide, and Fe(III) is reduced to Fe(II). 1 crystallizes in triclinic space group P-1 with a = 13.414(6) Å, b = 16.254(6) Å, c = 16.418(6) Å, α = 117.98(4)°, β = 94.49(3)°, γ = 107.61(4)° and Z = 1. Variable temperature magnetic measurements have demonstrated that very weak ferromagnetic interaction between the nearest paramagnetic CuII centers is exhibited. Thus weak ferromagnetic coupling might be transferred by –NC–Fe–CN– bridging units.The reaction of [Cu(DPA)]2+ moieties with each cyano ligand on ferricyanide results in the self-assembly of hepta-bimetallic complexes, [{Cu(DPA)(H2O)CN}4{Cu(DPA)CN}2Fe][PF6]8·4H2O. Very weak intercluster ferromagnetic coupling between the nearest paramagnetic Cu(II) ions is exhibited, and thus weak coupling might be mediated through the the –NC–Fe–CN– bridging units.Display Omitted► A new hepta-bimetallic complex has been formed. ► Weak intercluster ferromagnetic coupling is exhibited. ► Thus weak coupling might be mediated through the the –NC–Fe–CN– bridging units.
Keywords: Heptanuclear compound; Cyanide; Ferromagnetic interaction; Hexacyanoferrate;

Reaction of (trans-6,13-diamino-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane)nickel(II) perchlorate with oxalyl chloride in dimethylformamide forms trans-dichloro-(trans-6,13-dimethyl-6,13-bis(N,N-dimethylformamidinyl)-1,4,8,11-tetraazacyclotetradecane)nickel(II) diperchlorate dihydrate. This has a centrosymmetrical cation with nickel(II) in octahedral coordination by the four secondary amine nitrogen atoms of the macrocycle, and with chloride ions coordinated axially. The 6,13-diamino substituents have been converted to N,N-dimethylformamidinyl (―C―N+H=CH―N(Me)2) substituents, which are equatorially oriented. The N―C and C―N distances of the formamidinyl group are approximately equal, with bond angles about the C and two N atoms all near 120°, with the group ―C(Me)―NH―CH―N(Me)2 approximately coplanar, indicating approximately equal contributions from the canonical forms ―CH―NH―CH=N+(Me)2 and ―C―N+H=CH―N(Me)2.Reaction of (trans-6,13-diamino-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane)nickel(II) perchlorate with oxalyl chloride in DMF forms trans-dichloro-(trans-6,13-dimethyl-6,13-bis(N,N-dimethylformamidinyl)-1,4,8,11-tetraazacyclotetradecane)nickel(II) diperchlorate dihydrate, for which the structure was determined.Display Omitted► (trans-6,13-Diamino-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane)nickel(II) reacts with dimethylformamide and oxalyl chloride. ► The resulting macrocyclic ligand has 6,13-bis(N,N-dimethylformamidinyl) substituents. ► The structure of [trans-dichloro-{trans-6,13-dimethyl-6,13-bis-(N,N-dimethylformamidinyl)-1,4,8,11-tetraazacyclotetradecane}nickel(II)] diperchlorate dihydrate was determined. ► The canonical forms –CH–NH–CH = N+(Me)2 and –C–N+H = CH–N(Me)2 of the formamidinyl group contribute approximately equally to the structure.
Keywords: Nickel compound; Tetraaza macrocycle; N,N-dimethylformamidinium; N,N-dimethylformamidinyl; Crystal structure;

Structures and photocatalytic activities of metal-organic frameworks derived from rigid aromatic dicarboxylate acids and flexible imidazole-based linkers by Hua Qu; Ling Qiu; Xiao-Ke Leng; Miao-Miao Wang; She-Ming Lan; Li-Li Wen; Dong-Feng Li (1347-1351).
Three metal-organic frameworks based on the connectivity co-effect between rigid aromatic dicarboxylic acids and flexible linear linkers have been synthesized and characterized. [Cd(3-NO2-bdc)(bbi)]n (1) and [Co(3-NO2-bdc)(bbi)]n (2) (3-NO2-bdcH2  = 3-nitro-1,2-benzenedicarboxylic acid, bbi = 1,1′-(1,4-butanediyl)bis(imidazole)) are isostructural, which exhibit two-dimensional (2D) layer frameworks; [Co(3,5-pdc)(bbi)·2H2O]n (3) (3,5-pdcH2 = pyridine-3,5-dicarboxylic acid) has 2D 6-connected network with a Schäfli symbol of (344653). In addition, compounds 1 and 2 exhibit good photocatalytic activities under visible irradiation, and their different photocatalytic activities have also been analyzed based on the diffuse-reflectance UV/Vis spectra.Metal-organic frameworks 1 and 2, derived of rigid aromatic dicarboxylic acid and flexible linear linkers, are isostructural, which possess two-dimensional layer frameworks and exhibit good photocatalytic activities under visible irradiation. Different photocatalytic activities have been analyzed based on the diffuse-reflectance UV/Vis spectra.Display Omitted► Three metal-organic frameworks based on the connectivity co-effect between rigid aromatic dicarboxylic acids and flexible linear linkers have been synthesized. ► Compounds 1 and 2 exhibit good photocatalytic activities under visible irradiation. ► Different photocatalytic activities for 1 and 2 have been analyzed based on the diffuse-reflectance UV/Vis spectra.
Keywords: Metal-organic frameworks; Photocatalytic activity; Diffuse-reflectance UV/Vis spectra;

A reusable polymer supported copper(I) complex for the C–N bond cross-coupling reaction by S.M. Islam; Sanchita Mondal; Paramita Mondal; Anupam Singha Roy; Kazi Tuhina; Manir Mobarok (1352-1357).
The Ullmann coupling of amines with aryl iodide as well as arylboronic acids and N(H)-heterocycles with arylboronic acids has been carried out efficiently using PS-LCu(I) catalyst. The copper complex has been prepared and characterized by using scanning electron microscope (SEM), elemental analysis, atomic absorption spectroscopy (AAS), Thermo gravimetric analysis and spectrometric methods like Fourier transform infrared spectroscopy (FTIR). The effects of various parameters such as temperature, solvent and base on the reaction system were studied. The reusability experiments show that the catalyst can be used five times without much loss in the catalytic activity.The Ullmann coupling of amines with aryl iodide as well as arylboronic acids and N(H)-heterocycles with arylboronic acids have been carried out efficiently using polymer supported Cu(I) complex. The effects of various parameters were studied. The reusability experiments show that the catalyst can be reused five times.Display Omitted► Copper complex was synthesized from macroporous chloromethylated polystyrene. ► This catalyst shows excellent catalytic activity in N-arylation reaction. ► This catalyst shows excellent catalytic activity in amination reactions.
Keywords: PS-LCu(I) catalyst; N-arylation; Amination; Reusable catalyst;

The paper presents a combined experimental and computational study of the mononuclear oxorhenium(V) complex [ReOBr(hmbzim)(PPh3)2]Br·MeCN·H2O. The compound has been studied by IR, UV-Vis spectroscopy and X-ray crystallography. The electronic structure of [ReOBr(hmbzim)(PPh3)2]+ 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.A novel mononuclear oxorhenium(V) complex [ReOBr(hmbzim)(PPh3)2]Br·MeCN·H2O has been synthesized by IR, UV-Vis spectroscopy and X-ray crystallography. The electronic structure of [ReOBr(hmbzim)(PPh3)2]+ 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.Display Omitted► A novel mononuclear Re(V) oxocomplex of imidazole-derived ligand was synthesized. ► The compound was identified by IR, UV-Vis spectroscopy and X-ray analysis. ► The spectroscopic features of the complex were investigated by DFT and TDDFT.
Keywords: Oxorhenium(V) complexes; 2-Hydroxymethylbenzimidazole; X-ray structure; UV-Vis spectrum; DFT and TDDFT calculations;

Imidotungsten(VI) complexes with chelating phenols as ROMP catalysts by Juuso Hakala; Mikko M. Hänninen; Ari Lehtonen (1362-1364).
Tungsten(VI) complexes of the type [W(NPh)Cl3(L)] (L = chelating phenolate) were studied as catalyst precursors for ROMP of 2-norbornene, dicyclopentadiene and 5-vinyl-2-norbornene. These compounds form active catalysts when treated by ethyl magnesium bromide. Moreover, polymerisations can be run under ambient atmosphere without complicated inert atmosphere techniques. Synthesis and crystal structure of a new precursor complex [W(NPh)Cl3(LS)] (LS  = 2,4-di-tert-butyl-6-(phenylthiomethyl)phenolate) are also described.Imidotungsten(VI) complexes with chelating phenolates can be activated by ethyl magnesium bromide to catalyse ROMP of norbornene derivatives. Reactions can be run under ambient atmosphere to yield polymers with high cis-content.Display Omitted► Imidotungsten(VI) complexes with chelating phenolates catalyse ROMP of norbornene derivatives when activated by EtMgBr. ► Polymerisations can be run simply under ambient atmosphere. ► All polymers have a high cis-content.
Keywords: ROMP; Phenolate ligands; Tungsten; Catalysis;

“Fluoride molecular scissors”: A rational construction of new Mo(VI) oxofluorido/1,2,4-triazole MOFs by Ganna A. Senchyk; Andrey B. Lysenko; Harald Krautscheid; Konstantin V. Domasevitch (1365-1368).
New molybdenum(VI) oxofluoride-organic hybrids, [Mo2F2O5(tr 2 ad)] (1) and [Mo2F2O5(tr 2 ad 2 )] (2), supported by angular or linear N1,N2-(1,2,4-triazol-4-yl) bridges (tr 2 ad, 1,3-bis(1,2,4-triazol-4-yl)adamantane; tr 2 ad 2 , 3,3′-bis(1,2,4-triazol-4-yl)-1,1′-biadamantane), were prepared in an aqueous HF solution under hydrothermal conditions. The structure of the compounds includes dinuclear corner-sharing {Mo2F2O5} cores, in which two octahedral Mo ions are linked by one oxygen atom (Mo-O 1.90–1.92 Å) and two triazolyl groups (Mo-N 2.37–2.40 Å). The latter occupy the cis-positions in the {Mo2F2O5(tr)2} coordination clusters (“secondary building blocks”). Terminal fluoride and two “molybdenyl” oxygen atoms complete the coordination sphere of each molybdenum ions. In both cases the ligands show the maximal tetradentate mode connecting the adjacent inorganic units into a zigzag chain.The fluoride ions, as terminal ligands, were employed for the modification of inorganic subtopology of the metal oxide-organic frameworks (MOOFs).Display Omitted► Fluoride ligands terminate inorganic subconnectivity of metal oxide-organic frameworks. ► 1,2,4-triazoles are efficient ligands for bridging Mo(VI) ions. ► Adamantane is a suitable molecular platform for design of bitriazole tectons.
Keywords: Coordination polymers; Adamantane; 1,2,4-Triazole; Molybdenum(VI);

A new synthetic entry into tungsten(V) chemistry is presented: a dinuclear tungsten(III) compound, K3W2Cl9, is oxidized in conc. HX (X = Cl, Br) with a mild oxidizing agent, hydrazinium or hydroxylammonium chloride, to [WVOX4(H2O)] species. To identify the products formed, all compounds were authenticated using X-ray crystallography. The solid state structures of {(C4H9)4N}[WOCl4(H2O)] (1a), (Py2CH2)2[WOCl4(H2O)]3Cl (2a), (PicH)2[WOCl4(H2O)]Cl (3a), (Pic2CH2)2[WOCl4(H2O)]2[SnCl6] (4a), {(C4H9)4N}[WOBr4(H2O)] (1b) and (Py2CH2)2[WOBr4(H2O)]3Br (2b) (where PicH+ stands for protonated 4-methylpyridine, Py2CH2 2+ for N,N′-methylenedipyridinium cation, and Pic2CH2 2+ for N,N′-methylenedipicolinium cation) consist of the octahedrally-shaped [WOX4(H2O)] complex ions. The anions are distorted with the equatorial halido ligands bent down and away from the oxide. Due to the trans influence of the latter, the aqua ligands bind at longer bond distances. Coordinated halides, aqua ligands and counterions are engaged in hydrogen bonds which result in interesting intermolecular connectivities.Potassium enneachloridoditungstate(III) was oxidized in conc. HX (X = Cl, Br) with hydrazinium or hydroxylammonium chloride to [WVOX4(H2O)] species. X-ray structure analysis of a series of [WOX4(H2O)] compounds revealed various hydrogen bonding motifs.Display Omitted► Tungsten coordination chemistry. ► Oxidation of potassium enneachloridoditungstate(III) in conc. HX (X = Cl, Br) to aquatetrahalidooxidotungstate(V). ► X-ray structures of a series of [WVOX4(H2O)] compounds.
Keywords: Tungsten; Oxidotungsten(V) complexes; Hydrogen bonding; Crystal structures; Synthesis;

Some copper(I) complexes of the type [Cu(L)(PPh3)2]X (14) [where L  = 2-chloro-(5-trifluoromethyl-phenyl)-pyridine-2-ylethylene-amine; X = Cl, CN, ClO4 and BF4 ] have been prepared by the condensation of 3-amino-4-chloro-benzotrifluoride with 2-acetylpyridine followed by the reaction with [Cu(MeCN)2(PPh3)2]Cl, [Cu(MeCN)2(PPh3)2]CN, [Cu(MeCN)2(PPh3)2]ClO4 and [Cu(MeCN)2(PPh3)2]BF4. All the complexes 14 were characterized on the basis of elemental analysis, IR, UV–visible and 1H NMR spectral studies. The representative complex of the compound 3 has been characterized by single crystal X-ray diffraction which reveals that the central copper(I) ion assumes highly distorted tetrahedral geometry. All the complexes worked as effective catalyst for the amination of aryl halide.A series of copper(I) complexes have been prepared and characterized by elemental analyses, IR, UV–visible and 1H NMR spectroscopy. Single crystal X-ray diffraction study of [Cu(L)(PPh3)2]ClO4 shows highly distorted tetrahedral geometry. All the copper(I) complexes worked as effective catalyst for the amination of aryl halide.Display Omitted► Synthesis of mixed ligand copper(I) complexes. ► Characterization by elemental analysis, IR, UV–visible and 1H NMR spectral studies. ► X-ray diffraction of complex 3 reveals that the central copper(I) ion assumes highly distorted tetrahedral geometry. ► All the complexes worked as effective catalyst for the amination of bromobenzene.
Keywords: Mixed ligand; Copper(I) complexes; Single crystal X-ray diffraction; Amination of aryl halides;

A novel hexasubstituted organosilyl derivative based on trivacant tungstosilicate [(C4H9)4N]3[α-A-SiW9O34(CH3SiOH)6]·3H2O (1), was synthesized under phase-transfer conditions, by the reaction of the CH3SiHCl2 with Na10[α-SiW9O34]∙18H2O, which was characterized by IR spectrum, elemental analyses and X-ray single crystal diffraction. X-ray structural analysis reveals that 1 crystallizes in hexagonal space group R 3m , with lattice constants a =  26.0333(2) Å, b =  26.0333(2) Å, c =  13.7239(2) Å, V =  8055.02(15) Å3, and Z =  3, which consists of a trivacant Keggin moiety [α-A-SiW9O34]10−, on which six {CH3Si―} groups are grafted via six Si―O―W bridges, and that each of the six {CH3Si―} groups links with two adjacent ones through Si―O―Si bridges resulting in a unique flower basket-shaped polyoxoanion framework.A novel hexasubstituted organosilyl derivative based on trivacant tungstosilicate [(C4H9)4 N]3H[α-ASiW9O34(CH3SiO)6]·3H2O was synthesized under phase-transfer conditions. The compound displays an open flower basket-shaped framework.Display Omitted► A hexasubstituted organosilyl derivative based on trivacant POMs was synthesized. ► The compound has been characterized by IR spectrum, elemental analyses. ► The compound consists of a [α-A-SiW9O34]10− and a cyclic hexameric (CH3SiO)6 group. ► The polyoxoanion represents a novel flower basket-shaped open framework.
Keywords: Polyoxometalate; Hexasubstituted; organosilyl; Tungstosilicate;

Tri-i-propyltin(IV) and diorganotin(IV) derivatives of guanosine of the general formulae, i-Pr3Sn(HGuO).H2O and [R2Sn(O)(HGuO).H2O]n, where R = Me, n-Oct and Ph; H2GuO = Guanosine, have been synthesized by either sodium salt or azeotropic removal of water method. The bonding and coordination behavior in these derivatives are discussed on the basis of FT-IR, multinuclear 1H, 13C and 119Sn NMR and 119Sn Mössbauer spectroscopic studies. These investigations suggest that guanosine acts as monoanionic monodentate coordinating through O-2′ of the ribofuranose group. Diorganotin(IV) derivatives of guanosine have a polymeric structure with Sn―O―Sn bridges and cis-disposition of the organic groups in a distorted trigonal-bipyramidal geometry around the tin atom. 119Sn Mössbauer and 119Sn NMR spectral data of tri-i-propyltin(IV) derivative support a penta-coordinate distorted trigonal-bipyramidal structure having equatorial organic groups, and involving a water molecule and O-2′ of the ribofuranose group in the axial positions. Some extent of intermolecular hydrogen-bonding involving water or (OH) groups leading to some degree of polymerization could not be ignored. Tri-i-propyltin(IV) and diorganotin(IV) derivatives of guanosine exhibited very low anti-inflammatory activity (~ 7.51–9.21% inhibition) at 40 mg kg− 1 dose and LD50 values > 200 mg kg− 1 in albino rats.Tri-i-propyltin(IV) and diorganotin(IV) derivatives of guanosine have been synthesized and characterized. Diorganotin(IV) derivatives have a polymeric structure with Sn―O―Sn bridges, while tri-i-propyltin(IV) derivative has a distorted trigonal-bipyramidal structure with equatorial organic groups, and a water molecule and O-2′ of the ribofuranose group in the axial positionsDisplay Omitted► Interaction of tri-i-propyltin(IV) and diorganotin(IV) moieties with guanosine. ► Diorganotin (IV) derivatives have a polymeric structure with Sn-O-Sn bridges. ► Tri-i-propyltin(IV) derivative has a distorted trigonal-bipyramidal structure with equatorial organic groups. ► All of these derivatives exhibit very low anti-inflammatory activity in albino rats.
Keywords: Guanosine; Organotin(IV) compound; Anti-inflammatory agent; Nucleic acid constituent;

The μ 5-dpstc4−anions (H4dpstc = 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride) link CdII centers to generate a 2D bilayer with two kinds of channels, further, 2-dpe pillars (2-dpe =  trans-1,2-di(2-pyridyl)ethylene) extend such 2D bilayer into a novel (3,4,5)-connected trinodal network [Cd2(dpstc)(2-dpe)(H2O)3]n, which features unattached self-penetrating prototype and three types of channels in one direction. In addition, the luminescent property and thermal stability of the complex 1 have been also discussed.This work reports a new (3,4,5)-connected pillared-bilayer CdII-network, which features unattached self-penetrating fragment and three types of channels in one direction.Display Omitted► A 3D pillared-bilayer CdII-framework with three types of channels in one direction. ► A new (3,4,5)-connected (32.4)(66)(3.63.86) topology. ► Unattached self-penetrating prototype.
Keywords: CdII-complex; Pillared bilayer; Topology; Luminescent;

The one-electron reduction of a multi-centred iron(III) polyoxometallate. A pulse radiolysis study by Inna Popivker; Israel Zilbermann; Eric Maimon; Haim Cohen; Dan Meyerstein (1390-1392).
The single electron reduction of the complex [P8W48O184Fe16(OH)28(H2O)4]20− by the hydrated electron yields the mixed-valence complex [P8W48O184FeIIFeIII 15(OH)28–(H2O)4]21− which has an intervalence charge transfer band in the near I.R. This result points out that there is a strong interaction between the iron centres. The formation of [P8W48O184FeIIFeIII 15–(OH)28(H2O)4]21− is followed by the loss of the FeII centre and the rearrangement of the remaining Fe15 III cluster.The single electron reduction of the complex [P8W48O184Fe16(OH)28(H2O)4]20− by the hydrated electron yields the mixed-valence complex [P8W48O184FeIIFeIII 15(OH)28–(H2O)4]21− which has an intervalence charge transfer band in the near I.R.Display Omitted► Single-electron reduction of a multi-centred iron(III) polyoxometallate by the hydrated electron. ► Pulse radiolytic study ► Strong interaction between iron centres
Keywords: Polyoxometallates; Iron oxide nanocluster; Single electron reduction; Mixed-valence; Inter-valence charge transfer; Pulse-radiolysis;

A new iridium(III) complex with efficient photo- and electro-luminescent properties by Shimin Wang; Yun Duan; Chen-Xia Du; Yang-Jie Wu (1393-1395).
A new complex of Ir(pi)2(acac) (L = 2-(4-bromophenyl)-1-ethyl-1H-phenanthro[9,10-d]imidazole) was designed and synthesized. Its molecular structure was determined by a single-crystal X-ray diffraction analysis. The Ir(III) complex showed characteristic phosphorescence with an emission of 570 nm and a high quantum efficiency of 28%. A high performance yellow OLEDs was successfully fabricated by using this Ir(III) complex as dopant.A new iridium(III) complex of Ir(pi)2(acac) (pi = 2-(4-bromophenyl)-1-ethyl-1H-phenanthro[9,10-d]imidazole) with efficient photo- and electro-luminescent properties was conveniently synthesized and characterized by X-ray crystallography.Display Omitted► Syntheses of iridium complex Ir(pi)2(acac) with the 2-(4-bromophenyl)-1-ethyl-1H-phenanthro[9,10-d]imidazole ligand. ► Crystallographic characterization of the Ir(pi)2(acac) was studied. ► Ir(pi)2(acac) is a promising phosphorescent material for OLEDs.
Keywords: Iridium(III) complexes; Phosphorescence; Crystal structure; Electroluminescence;

Three novel microporous 3D heterometallic 3d–4f coordination polymers: Synthesis, crystal structures and photoluminescence properties by Shan-Tang Yue; Zhi-Qiang Wei; Ning Wang; Wen-Jing Liu; Xia Zhao; Li-Mei Chang; Ying-Liang Liu; Hai-Hong Mo; Yue-Peng Cai (1396-1399).
Three novel 3D microporous heterometallic coordination polymers, [LnZn(imdc)(ip)(H2O)2]·3H2O [Ln = Nd (1), Eu (2), Gd (3); H3imdc = imidazole-4,5-dicarboxylic acid; ip = isophthalate], have been synthesized under hydrothermal conditions. X-ray crystal structure analyses reveal that compounds 1–3 are isomorphous and crystallize in the monoclinic space group P21/c. The crystal structures constructed from Zn-imdc step-like chains and 2D [LnZn(imdc3−)]n layers and ip ligand, which giving rise to a 3D framework that consists of two types of 1D open channels, with 5.2 × 8.6 Å channels along the a axis and 8.6 × 10.2 Å channels along the b axis. The luminescence properties of complex 1 and 2 have also been investigated.The crystal structures constructed from Zn-imdc step-like chains and 2D [NdZn(imdc3−)]n layers and ip ligand, which giving rise to a 3D framework that consists of two types of 1D open channels, with 5.2 × 8.6 Å channels along the a axis and 8.6 × 10.2 Å channels along the b axis.Display Omitted► Three novel 3D microporous heterometallic coordination polymers have been synthesized. ► 3D framework consists of two types of 1D open channels. ► Complexes constructed from H3imdc and Ln–Zn heterometallic system have not been reported.
Keywords: Hydrothermal synthesis; Heterometallic; Microporous; Luminescence;

The Zn(II)-organic coordination polymers based on 2-(pyridin-4-yl)-1H-imidazole-4,5-dicarboxylate ligands: Crystal structures and luminescent properties by Shu-Quan Zhang; Fei-Long Jiang; Ming-Yan Wu; Rui Feng; Jie Ma; Wen-Tao Xu; Mao-Chun Hong (1400-1405).
Two novel compounds, [Zn(H2PIDC)2(H2O)2] (1) and [Zn4(PIDC)2(SO4)(H2O)5]·(2.5H2O) (2) (H3PIDC = 2-(pyridin-4-yl)-1H-imidazole-4,5-dicarboxylic acid) have been synthesized under hydrothermal condition, and characterized by thermal analyses (TGA), powder X-ray diffractions (PXRD), and single-crystal X-ray diffractions, respectively. Compound 1 is constructed from mononuclear molecules which form the 2D square networks and further extend to 3D supermolecular framework through the π–π stacking and strong hydrogen bonding interactions. Compound 2 exhibits a 3D framework and generates the 1D open rhombic channels filled with the coordinated water molecules, sulfate anions and free water molecules. The structure of 2 can be rationalized as a (4,4,4)-connected net and shown as a unique (4.53.6.7)4(42.52.72)2(52.62.72) topology. The different luminescent nature for 1 and 2 may be due to their various delocalization environments.2-(pyridin-4-yl)-1H-imidazole-4,5-dicarboxylaic-Zn(II) complexes were obtained, involving a 3D supermolecular framework constructed from 0D monomer linked by H-bonds and π-π interactions, and a unique (4,4,4)-connected topologic 3D framework with 1D open channels. Effect of delocalization environment of the ligands on emission spectrum has been discussed.Display Omitted► Two kinds of Zn(II) salts reacting with the ligand H3PDCI yield two new complexes. ► Compound 2 exhibits a unique (4,4,4)-connected net topology. ► The delocalization environment of ligand has a great effect on emission spectrum.
Keywords: Zn(II); Coordination polymers; Hydrothermal synthesis 2-(pyridin-4-yl)-1H-imidazole-4,5-dicarboxylaic; (4,4,4)-connected net; Luminescence;

Two novel Zn(II) coordination polymers based on a carboxylate functionalized imidazophenanthroline derivative ligand by Zhen-Hua Yang; Xian-Feng Xiong; Huai-Ming Hu; Yang Luo; Li-Han Zhang; Qiao-Hong Bao; Yi-Qing Shang-Guan; Gang-Lin Xue (1406-1409).
Two novel zinc(II) coordination polymers, [Zn2(Hcpip)2(ox)]n·2nH2O (1) and [Zn4(Hcpip)2(cpip)2(ox)]n·5nH2O (2), (H2cpip = 2-(2-carboxyphenyl) imidazo [4,5-f]1,10-phenanthroline, H2ox = oxalic acid), have been hydrothermally synthesized and characterized by elemental analysis, IR, single crystal X-ray diffraction. Compound 1 is a 1D chain, in which the dinuclear [Zn2(Hcpip)2]2+ units are linked through (ox)2− anions. Compound 2 is a 2D layer structure, which is constructed from the 1D chains bridged by (ox)2− anions. These two compounds possess strong luminescence and good thermal stabilities.Two novel zinc(II) coordination polymers, [Zn2(Hcpip)2(ox)]n·2nH2O (1) and [Zn4(Hcpip)2(cpip)2(ox)]n·5nH2O (2), (H2cpip = 2-(2-carboxyphenyl) imidazo [4,5-f]1,10-phenanthroline, H2ox = oxalic acid), have been hydrothermally synthesized and characterized. These two compounds possess strong luminescence and good thermal stabilities.Display Omitted► 1. Two different novel zinc(II) coordination polymers, [Zn2(Hcpip)2(ox)]n·2nH2O (1) and [Zn4(Hcpip)2(cpip)2(ox)]n·5nH2O (2), have been hydrothermally synthesized by controlling the pH values. ► 2. The dinuclear zinc(II) units are linked through oxalate anions to form 1D and 2D coordination polymers 1 and 2. ► 3. The 3D supramolecular structures are constructed by hydrogen bonding and ππ stacking interactions. ► 4. Coordination polymers 1 and 2 possess strong luminescence and good thermal stabilities.
Keywords: Zinc; Hydrothermal synthesis; Coordination polymer; Crystal structure; Luminescent property;

Tunable structures aroused by cation exchange reaction of solvent-mediated mechanism by Chunying Xu; Xianjuan Wang; Degang Ding; Hongwei Hou; Yaoting Fan (1410-1413).
In our efforts to tune structure by cation exchange reaction, a rare 1-D meso-helical chain [CdL(Ac)2] n (1) was immersed into the methanol solution of Hg(Ac)2, and then new crystals of {[HgL0.5(Ac)2]·(CH3OH)} n (2) (L = 1,4-bis(2-methylbenzimidazol-1-ylmethyl) benzene) were obtained on the surface of 1. Single crystal X-ray analysis reveals that complex 2 shows a 1-D zigzag chain, in which the mercury ion adopts an unprecedented six-coordinated mode in binuclear unit. Notably, the framework of 2 is completely different from that of 1. In addition, the determination of Scanning Electron Microscope and Energy-Dispersive X-ray Spectrometry reveals that the exchange is a recurrent dissolving-exchange-crystallization process of solvent-mediated mechanism. This work provides a new effective tactic of adjusting molecular structures.Through cation exchange reaction, a meso-helical Cd(II) chain has been adjusted to a zigzag Hg(II) chain with an unprecedented coordination mode. The results prove that the exchange is a recurrent dissolving-exchange-crystallization process of solvent-mediated mechanism by visual evidence. This work provides a new effective tactic of adjusting molecular structures.Display Omitted► Tune structure from a meso-helical Cd(II) chain to a zigzag Hg(II) chain by cation exchange reaction. ► The exchange is a recurrent dissolving-exchange-crystallization process with a solvent-mediated mechanism. ► A new effective tactic of adjusting molecular structures.
Keywords: Tunable structure; Ion exchange reaction mechanism; Mercury complex;

Two novel iridium(III) complexes containing 2-(4,6-difluorophenyl)pyridyl cyclometalating ligand and amidate ancillary ligands were synthesized and characterized by NMR and X-ray crystallographic methods. Photophysical properties including UV–vis absorption and photoluminescence spectra were studied, indicating that the electronic properties of the amidate ancillary ligand exhibit a significant effect on the emitting excited states of these iridium(III) amidate complexes and thus lead to different emission colors.Two new photoluminescent iridium(III) 2-(4,6-difluorophenyl)pyridyl complexes containing N-phenylbenzamidate and N-phenylacetamidate ancillary ligands were synthesized and characterized. Photophysical property studies show that the electronic properties of amidate ancillary ligand exhibit a critical effect on the emission color of the Ir(III) amidate complexes.Display Omitted► Ir(III) 2-(4,6-difluorophenyl)pyridyl complexes with amidate ancillary ligand. ► Tuning emission color by simply altering the structure of amidate ligand. ► Amidate ligands affect the energy level of emitting excited states. ► Amidate ligands affect inter-ligand energy transfer.
Keywords: Iridium complex; Amidate; Photoluminescence; 2-(4,6-difluorophenyl)pyridine; Heteroleptic complex;

MnIII–Salen composite materials based on Keggin heteropolyanions exhibiting photocatalytic and electrocatalytic activities by Xing Meng; Hai-Ning Wang; Guang-Sheng Yang; Shuang Wang; Xin-Long Wang; Kui-Zhan Shao; Zhong-Min Su (1418-1421).
Two new inorganic–organic hybrid supramolecular compounds based on Keggin-type polyoxoanions, namely [Mn(salen)(CH3OH)2]3[PMo12O40] (1) and [Mn(salen)(CH3OH)2]3[PW12O40] (2) (H2salen = N,N′-ethylenebis(salicylideneimine)) have been synthesized and characterized by single-crystal X-ray diffraction analysis, elemental analysis, IR spectroscopy, and TG analysis. Two compounds reported herein represent the first examples of integrating metal–Schiff-base segments with Keggin polyanions characterized via single-crystal X-ray diffraction. Such hybrid materials display photocatalytic and electrocatalytic bifunctional catalytic activities.Two new inorganic–organic hybrid supramolecular compounds, namely [Mn(salen)(CH3OH)2]3[PMo12O40] (1) and [Mn(salen)(CH3OH)2]3[PW12O40] (2) (H2salen = N,N′-ethylenebis(salicylideneimine)) have been successfully synthesized. They represent the first examples of integrating metal–Schiff-base segments with Keggin heteropolyanions characterized via single-crystal X-ray diffraction which display photocatalytic and electrocatalytic bifunctional catalytic activities.Display Omitted► Two new inorganic–organic hybrid supramolecular compounds have been synthesized. ► They are successfully characterized via single-crystal X-ray diffraction. ► These compounds represent the first examples of integrating metal–Schiff-base segments with Keggin heteropolyanions. ► Both display photocatalytic and electrocatalytic bifunctional catalytic activities.
Keywords: Inorganic–organic hybrid material; Metal–Schiff-base; Keggin polyanions; Catalytic activity;

A family of novel cationic ruthenium complexes [RuHL(PAr3)2]Cl (Ar = phenyl, p-methoxyphenyl, and p-trifluoromethylphenyl; L = 2,6-bis(1,5-diphenyl-1H-pyrazol-3-yl)pyridine) has been synthesized and characterized by IR, 31P{1H} NMR, 1H NMR and elemental analyses. The [RuHL(PPh3)2]Cl was further identified by X-ray crystallography. These complexes exhibit good to excellent catalytic activities for the transfer hydrogenation of ketones in refluxing 2-propanol, and the highest TOF is up to 3534 h− 1. The effect of electronic factors of these complexes on the transfer hydrogenation of ketones reveals that the catalytic activity is promoted by the electron-withdrawing phosphine.A family of novel cationic complexes [RuHL(PAr3)2]Cl (Ar = phenyl, p-methoxyphenyl, p-trifluoromethylphenyl; L = 2,6-bis(1,5-diphenyl-1H-pyrazol-3-yl)pyridine) has been synthesized and they exhibited good to excellent catalytic activities in the transfer hydrogenation of ketones.Display Omitted► A family of novel cationic ruthenium hydride complexes has been synthesized and characterized. ► Ruthenium hydride complexes are efficient catalysts in the transfer hydrogenation of ketones. ► The effect of electronic factor of the phosphine on the catalytic activity is originally revealed.
Keywords: Ruthenium; Phosphine; Tridentate nitrogen; Transfer hydrogenation; Ketone;

An ionic metal–dithiolene complex, 1,1'-didecyl-4,4'-bipyridinium bis(maleonitriledithiolato)zincate(II) ([Zn(mnt)2]2−), was synthesized and characterized by elemental analysis, infrared spectroscopy and crystal structure. In the [Zn(mnt)2]2− moiety, the complex shows distorted tetrahedral geometry with Zn2+ coordinated to four S-atoms from two mnt2− ligands, and its long molecular axis adopts a similar orientation with 1,1'-didecyl-4,4'-bipyridinium. Two distinguishable redox processes occur in the voltage region of − 1.0 to 1.0 V, with the irreversible and reversible redox couples corresponding to [Zn(mnt)2]2−/[Zn(mnt)2] •− and 1,1'-didecyl-4,4'-bipyridinium •+/1,1'-didecyl-4,4'-bipyridinium2+, respectively. An uncommon nematic mesophase behavior in this complex was confirmed by polarized-light optical microscopy (POM) and differential scanning calorimetry (DSC) measurements.An uncommon nematic mesophase behavior was observed in a charge transfer salt consisted of bis(maleonitriledithiolato)zincate dianion with 1,1'-didecyl-4,4'-bipyridiniumDisplay Omitted► A viologen derivative, 1,1'-didecyl-4,4'-bipyridinium, as liquid crystal architecture. ► A charge-transfer-salt-type ionic liquid crystal. ► Ionic liquid crystal shows nematic mesophase. ► Formation of mesophase arises from the hydrocarbon chain melting.
Keywords: Bis(maleonitriledithiolato)zincate dianion; 1,1'-didecyl-4,4'-bipyridinium; Electrochemical property; Mesophase;

An unprecedented mixed-valence Cu(I)/Cu(II) metal-organic framework {[Cu2(HPhIDC)(OH)]·H2O}n (H3PhIDC = 2-phenyl-1H-imidazole-4,5-dicarboxylic acid) (1) has been solvothermally synthesized and structurally characterized by elemental analysis, IR spectroscopy, XPS spectrum and single crystal X-ray diffraction analysis. In 1, each Cu(I) ion is two-coordinated by imidazole and OHunits. The HPhIDC2−ligands connect Cu(II) ions leading to a one-dimensional chain structure. The thermal properties of 1 are reported.A rare metal-organic framework {[Cu2(HPhIDC)(OH)]·H2O}n (1) has been solvothermally synthesized and characterized by elemental analysis, IR spectroscopy, XPS spectrum and single crystal X-ray diffraction analysis. It is the first example of mixed-valence copper polymer constructed from 2-phenyl-1H-imidazole-4,5-dicarboxylic acid (H3PhIDC) and Cu(ClO4)2.Display Omitted► An unprecedented mixed-valence Cu(I)/Cu(II) metal-organic framework. ► 2-phenyl-1H-imidazole-4,5-dicarboxylic acid reacts with Cu(ClO4)2 under thermal conditions. ► The polymer has structurally characterized by elemental analysis, IR spectrum, XPS spectrum and single crystal X-ray diffraction analysis. ► The themostabilities of the polymer have been determined.
Keywords: Mixed-valence; Copper; Polymer; Phenyl imidazole dicarboxylate; Crystal structure;

Mono-, di-, and tri-nuclear gold(I) complexes with dansyl moiety: Synthesis, characterization, and photophysical properties by Hsiu-Yi Chao; Bo-Chao Su; Cheng-Luan Li; Chi-Keung Lam; Xiao-Long Feng (1436-1439).
Mono-, di-, and tri-nuclear gold(I) complexes with dansyl group (dansyl = 5-dimethylamino-naphthalene-1-sulfonyl), 13, have been synthesized and their photophysical properties investigated. The crystal structures of complexes 2 and 3 were determined by X-ray diffraction.Mono-, di-, and tri-nuclear gold(I) complexes with dansyl group, 13, have been synthesized and characterized. Their photophysical properties were studied.Display Omitted► Mono-, di-, and tri-nuclear gold(I) complexes with dansyl group were synthesized. ► Weak to significant gold⋯gold interactions exist in complexes 2 and 3. ► Complexes 13 show intense luminescence in the solid state at 298 K.
Keywords: Dansyl; Gold; Luminescence; Synthesis;

Different types of structure among the transition metal complexes of 1,4-naphthalene di-(2-oxyacetate) (L) are observed. Cobalt(II) 1,4-naphthalene di-(2-oxyacetate) complex is a tetranuclear complex. This tetranuclear complex is formed by interlinking two dinuclear cobalt cores having aqua and carboxylate bridges. Dinuclear cores of this complex break down on reaction with pyridine (py) molecules to form a coordination polymer having mononuclear repeat units. One of the carboxylate group of L bridges two manganese ions of manganese(II) 1,4-naphthalene di-(2-oxyacetate) coordination polymer and other carboxylate end of the ligand remains uncoordinated. A spiral five coordinated carboxylate coordination polymer having [Cu(H2O)(py)2] as connecting nodes to two ends of monodentate carboxylate of L is prepared and characterised.Cobalt(II) 1,4-naphthalene di-(2-oxyacetate) is a tetranuclear complex. It reacts with pyridine to form coordination polymer. Manganese (II) and copper (II) 1,4-naphthalene di-(2-oxyacetate) are coordination polymer, former has one side of the ligand uncoordinated and later is a five coordinated spiral coordination polymer.Display Omitted► Varieties in structural features of coordination complex and polymers of flexible carboxylic acid are shown. ► Example of aqua bridged cobalt binuclear units acting as node to form tetranuclear complex is shown. ► A manganese dicarboxylate coordination polymer with one carboxylate end bridging is demonstrated. ► Square pyramid geometry around copper (II) ions guide formation of spiral coordination polymer.
Keywords: Flexible dicarboxylic acid; Tetranuclear complex; Coordination polymer; Spiral structure; Aqua-bridged dinuclear core;

A novel coordination polymer, [Cu5(IBA)4(N3)2(SO4)2]·4H2O (1) (HIBA = 4-(imidazol-1-yl)-benzoic acid), has been synthesized under hydrothermal condition, and characterized by elemental analysis, IR and single-crystal X-ray diffraction. X-ray single-crystal structural analyses reveal that complex 1 exhibits a two-dimensional layer structure based on pentanuclear Cu(II) clusters, and further assembled into a three-dimensional supramolecular structure via weak intermolecular interaction with one-dimensional open channels, in which the lattice water molecules are located. Moreover, variable-temperature magnetic susceptibility studies indicate dominant ferromagnetic interactions within the pentanuclear cluster.A novel coordination polymer, [Cu5(IBA)4(N3)2(SO4)2]·4H2O, has been synthesized, which exhibits a two-dimensional layer structure based on pentanuclear Cu(II) clusters. Variable-temperature magnetic susceptibility studies indicate dominant ferromagnetic interactions within the pentanuclear cluster.Display Omitted► The coordination polymers based on the ligands containing both imidazole and carboxylate group are scarce so far. ► Complex 1 exhibits a rare two-dimensional layer structure based on pentanuclear Cu(II) secondary building units. ► Magnetic susceptibility studies indicate dominant ferromagnetic interactions within the pentanuclear cluster.
Keywords: Cu(II) coordination polymer; Crystal structure; Pentanuclear; Magnetism;

Two novel polyoxotantalates formed by Lindqvist-type hexatantalate and Copper-amine complexes by Gui-Ling Guo; Yan-Qing Xu; Bao-Kuan Chen; Zheng-Guo Lin; Chang-Wen Hu (1448-1451).
Two novel polyoxotantalate derivatives, {[Cu(1,3-dap)2]2[Cu(1,3-dap)(H2O)]2[Ta6O19]}·8H2O (1) and [Cu(en)2]4[Ta6O19]·14H2O (2) (1,3-dap = 1,3-diaminopropane, and en = ethylenediamine), which are constructed from the Lindqvist-type [Ta6O19]8− anion and copper–amine complexes, have been synthesized and characterized by elemental analyses, IR, XPS, TGA and single-crystal X-ray diffraction. In compound 1, each [Ta6O19]8− anion is bound to four copper fragments via the surface bridging oxygen atoms to form a neutral tetrasupported Lindqvist structure, which is further connected by water trimer via hydrogen-bonds to yield a one-dimensional (1D) supramolecular chain. In compound 2, the [Ta6O19]8− anions are linked together via the hydrogen bonds and Cu⋯O weak interaction to form an infinite 1D supramolecular chain, which is further connected to each other via hydrogen bonds with the cyclic water tetramer to yield a two-dimensional (2D) supramolecular network.The [Ta6O19]8− anions in 2 are connected by Cu⋯O weak interactions and extensive O―H⋯O hydrogen-bonding interactions to form a 2D supramolecular network.Display Omitted► Transition metal complexes were first introduced into the system of polyoxotantalates. ► 1 represents the first hexatantalate coordinated with four copper–amine complexes. ► There exist water trimer and water tetramer in 1 and 2, respectively. ► There are extensive hydrogen bonds between water clusters and polyanions in 1 and 2.
Keywords: Polyoxotantalate; Lindqvist-type; Polyoxometalates; Supramolecular; Water trimer; Water tetramer;

Three isostructural mononuclear iron(II) complexes with the similar tripodal ligands had been synthesized and structurally characterized, which exhibit three-dimensional (3D) supramolecular network constructed by S···H―C hydrogen bonding interactions between adjacent iron centers. The variable-temperature magnetic properties of these three complexes under different pressure have been investigated to probe the possibilities of spin transition behavior under external pressure. For 1, the pressure-driven SCO behavior was firstly observed as the application of external pressure, and then the pressure-driven thermal SCO behavior occurs subsequently as the external pressure reached up to a specific value. However, for 2 and 3, no any SCO behaviors could be observed even under high external pressure. Comparison of the crystal structures of the three complexes show that the differences are mostly due to steric effects and weak ligand field originated from the similar tripodal ligands.Three isostructural mononuclear iron(II) complexes with the similar tripodal ligands have been synthesized. Interestingly, for compound 1, the pressure-driven SCO behavior was firstly observed as the application of external pressure, and then the pressure-driven thermal SCO behavior occurs subsequently as the external pressure reached up to a specific value.Display Omitted► Three mono-nuclear iron(II) complexes with the typical FeN6 octahedron were synthesized. ► Pressure-driven SCO behavior and then the pressure-driven thermal SCO behavior occurs separately as the external pressure increasing. ► The fraction of HS-Fe(II) state was quantitatively decreasing along with the change of pressure at specific temperature.
Keywords: Iron(II) complexes; Spin crossover; Pressure-driven; Tripodal ligand;

Zinc complexes supported by NN-bidentate AA Bn ligand (AA Bn -H = (E)-N-[2-(benzyliminomethyl)phenyl]-2,6-diisopropylaniline) are synthesized and fully characterized. The reaction of diethyl zinc (ZnEt2) with AA Bn -H (1.1 mol equiv) yields three-coordinated mono-adduct zinc complex [(AA Bn )ZnEt] (1). However, treatment of AA Bn -H with ZnEt2 in the same stoichiometric proportion in the presence of 4-dimethylaminopyridine (DMAP, one equiv) affords [(AA Bn )Zn(DMAP)Et] (2) as the tetra-coordinated monomeric zinc complex. Bis-adduct complex [(AA Bn )2Zn] (3) results from treatment of ZnEt2 with AA Bn -H (two equiv) in refluxing toluene in high yield. Complexes 1 and 3 are efficient catalysts for the ring-opening polymerization (ROP) of ε-caprolactone (ε-CL) in the presence of alcohol. The “controlled” character of Zn complex 1 also enabled preparation of the PEG-b-PCL copolymer.Novel zinc complexes supported by the NN-bidentate anilido-aldimine (AA Bn) ligand are synthesized and fully characterized. Complex [(AA Bn )ZnEt] (1) catalyzes the ring-opening polymerization of ε-caprolactone in the presence of 9-anthracenemethanol with the highest activity in a controlled manner among these Zn complexes.Display Omitted► Zinc complexes incorporating the AA Bn ligand are synthesized and fully characterized. ► Complex 1 catalyzes the polymerization of ε-caprolactone with the highest activity among these Zn complexes. ► Complex 1 catalyzes the polymerization of ε-caprolactone in a “controlled” manner.
Keywords: Zinc complex; Catalyst; NN-bidentate; Anilido-aldimine; Ring-opening polymerization; ε-caprolactone;

Conformational change of ternary copper(II) complexes of cationic Schiff-bases and N-heteroaromatic amines induced by intercalative binding to DNA by Yusuke Iwasaki; Masato Kimura; Atsushi Yamada; Yuichiro Mutoh; Maiko Tateishi; Hidekazu Arii; Yusuke Kitamura; Makoto Chikira (1461-1464).
DNA-fiber EPR spectra revealed that intercalative binding of the ternary copper(II) complexes of cationic Schiff-bases and N-heteroaromatic amines induced the rearrangement of coordination spheres of the complexes from tetragonal pyramidal to square planar geometries. The binding of the complexes was also characterized by UV–vis, CD and fluorescence spectroscopy together with DFT calculation of the conformational change. The synergetic effect of the intercalation, the electrostatic interaction and the rearrangement of the coordination spheres enhanced the oxidative and the photodynamic DNA cleavage activities.DNA-fiber EPR spectra revealed that intercalative binding of the ternary copper(II) complexes of cationic Schiff-bases and N-heteroaromatic amines induced the rearrangement of coordination spheres of the complexes from tetragonal pyramidal to square planar geometries.Display Omitted► Ternary Cu(II) complexes of cationic Schiff-bases and N-heteroaromatic amines. ► Intercalation to DNA induced conformational change of the coordination spheres. ► The synergetic effect of intercalation, electrostatic interaction and the conformational change. ► Enhancement of the oxidative and photodynamic DNA cleavages.
Keywords: DNA-fiber EPR; Cationic Schiff-base copper(II) complex; DNA photo-cleavage; DNA binding structure; Conformational change on DNA;

A new 3D hybrid architecture containing Keggin-type tungstosilicate and Cu4(EGTA)2 metallamacrocyclic cation by Chun-Hua Zhang; Chun-Jing Zhang; Ya-Guang Chen; Shu-Xia Liu (1465-1468).
A new three-dimensional (3D) hybrid compound [Cu4(EGTA)2(H2O)4Cu2(H2O)8][SiW12O40]·14H2O (1), [EGTA = ethyleneglycol-bis-(2-aminoethylether)-tetra acetic acid], was conventionally synthesized and characterized by elemental analysis, IR, TG, and single crystal X-ray diffraction. In 1, the square inorganic layers formed by the coordination of tungstosilicate anions to copper ions are supported by Cu4(EGTA)2 metallamacrocyclic cations, giving a unique 3D framework with α-Po topology. Additionally, luminescent and magnetic properties of 1 are investigated in the solid state.A new hybrid compound [Cu4(EGTA)2(H2O)4Cu2(H2O)8][SiW12O40]·14H2O (1) was conventionally synthesized and characterized, in which the square inorganic layers formed by the coordination of tungstosilicate anions to copper ions are supported by bidentate Cu4(EGTA)2 metallamacrocyclic cations giving a unique 3D framework with α-Po topology.Display Omitted► A unique 3D α-Po framework is formed by SiW12–Cu layers and Cu4(EGTA)2 cations. ► The use of the multidentate multicarboxyl flexible ligand EGTA is important and effective. ► The luminescent and magnetic properties of compound 1 have been studied.
Keywords: Polyoxometalate; Multicarboxylic ligand; Luminescence; Magnetic property;

Paramagnetic metal complexes sometimes exhibit no appreciable 13C NMR signals due to the short relaxation time. By making use of the fast self-exchange electron transfer between paramagnetic [FeIII(TPrP)(tBuNC)2]ClO4 and the corresponding diamagnetic [FeII(TPrP)(tBuNC)2], we have determined the chemical shifts of the carbon atoms that exhibit no signals due to the considerable amount of spin density. We have also determined the spin density of the meso carbon atom in [FeIII(TPrP)(tBuNC)2]ClO4 to be 0.076, which is to our knowledge the largest among all the low-spin iron(III) porphyrin complexes reported previously. This method is applicable to all the low-spin iron(III) porphyrinoids if the corresponding diamagnetic complexes are available.The chemical shifts of the peripheral carbon atoms in 1, which exhibit no appreciable 13C NMR signals due to the radical character of the complex, were determined by making use of the fast self-exchange electron transfer between low-spin iron(III) and the corresponding diamagnetic iron(II) porphyrin complex.Display Omitted► Formation of the low-spin iron(III) complex of meso-tetrapropylporphyrin complex carrying tert-butylisocyanide as axial ligand. ► Methodology to determine the NMR chemical shifts of the carbon atoms with radical characters. ► Determination of the spin densities on the peripheral atoms on the basis of the 13C NMR and 1H NMR chemical shifts.
Keywords: Iron porphyrin; 13C NMR; Spin density; Self-exchange electron transfer; Electron configuration;

Assembly of oximate-bridged Mn6 cluster to a one-dimensional chain by Guang-Yu An; Ai-Li Cui; Hui-Zhong Kou (1475-1478).
Hexanuclear [MnIII 6O2(Hsalaox)6(MeOH)4(MeCO2)2]·4MeOH·2H2O (1) and polymeric [MnIII 6O2(Hsalaox)6(MeOH)6(tp)]·12H2O (2) are prepared by the reaction of Mn2+, salicylamidoxime (H3salaox) and corresponding carboxylates (tp2−  = terephthalate). Magnetic studies show that both complexes display slow magnetization relaxation.Hexanuclear [Mn6O2(Hsalaox)6]2+ fragments can form discrete clusters and a terephthalate-bridged 1D chain, which display slow magnetization relaxation.Display Omitted► Salicylamidoxime as the ligand for polynuclear Mn6 complexes. ► Terephthalic acid as the bridging ligand for polymeric coordination compound. ► Novel 1D complex that contains hexanuclear Mn(III) as nodes. ► Slow relaxation of magnetization for two compounds has been observed. ► No obvious improvements in magnetism by changing Mn6 to 1D.
Keywords: Crystal structure; One-dimensional; Oximato bridge; Polynuclear; Magnetic properties;

Temperature-induced two copper (II) supramolecular isomers constructed from 2-ethyl-1H-imidazole-4, 5-dicarboxlylate by Zhi-Gang Gu; Guo-Zhen Li; Pei-Yi Yin; Yue-Nan Chen; Hui-Min Peng; Ming-Fang Wang; Fang Cheng; Feng-Long Gu; Wei-Shan Li; Yue-Peng Cai (1479-1484).
Two copper (II) supramolecular isomers 1a and 1b formulated as [Cu(H2EDC)2]n (H3EDC = 2-ethyl-1H-imidazole-4,5-dicarboxlylate) have been hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction. Coordination modes, hydrogen bonding interactions and stacking modes are different in the two isomers. Meanwhile, luminescent properties of the complexes were studied.Two copper (II) supramolecular isomers (1a and 1b) have been hydrothermally synthesized via reaction of 2-ethyl-1H-imidazole-4,5-dicarboxlylate and CuCl2 under different temperature. The results reveal that 1a presents slipped ABAB… packing mode while 1b contains AAAA…mode. Meanwhile, luminescent properties of the complexes were studied.Display Omitted► Two copper (II) supramolecular isomers (1a and 1b) have been synthesized from 2-ethyl-1H-imidazole-4, 5-dicarboxlylate. ► The results reveal that 1a presents slipped ABAB… packing mode while 1b contains AAAA…mode.
Keywords: Supramolecular isomers; Temperature-induced; Stacking modes; Luminescent properties;

A novel coordination polymer of sodium [Na2(Pzta)2(H2O)2]n (1) has been synthesized hydrothermally by reacting pyrazine carbonitrile and sodium azide in the presence of aluminum(III) chloride as Lewis acid catalyst. Complex 1 was characterized by elemental analysis, thermal gravimetric analysis and IR spectroscopy. Single crystal X-ray diffraction revealed that complex 1 has both distorted trigonal bipyramidal and square pyramidal coordination geometries around sodium atoms. Complex 1 represents the first hydrothermally synthesized 1D sodium monotetrazole coordination polymer. Strong hydrogen bonds are formed between water molecules and nitrogen atoms of both pyrazine and tetrazole rings which result in the formation of a 2D metallosupramolecular network. The luminescence properties of 1 were also investigated at room temperature in the solid state.A novel coordination polymer of sodium [Na2(Pzta)2(H2O)2]n (1) has been synthesized hydrothermally by reacting pyrazine carbonitrile and sodium azide in the presence of aluminum(III) chloride as Lewis acid catalyst. Single crystal X-ray diffraction revealed that complex 1 has both distorted trigonal bipyramidal and square pyramidal coordination geometries around sodium atoms. Complex 1 represents the first hydrothermally synthesized 1D sodium monotetrazole coordination polymer. Strong hydrogen bonds are formed between water molecules and nitrogen atoms of both pyrazine and tetrazole rings which result in the formation of a 2D metallosupramolecular network. The luminescence properties of 1 were also investigated at room temperature in the solid state.Display Omitted► Complex 1 has high thermal stability and is virtually insoluble in most common solvents such as acetone, methanol, chloroform, benzene, water etc. along with the impressive emission properties making it a potential photoactive material. ► In the polymeric structure of 1, hydrogen bonds working in cooperativity with covalent interactions are capable of ‘maneuvering’ complex ions into desirable motifs. ► This is the first report in the family of sodium tetrazolate MOFs where the metal has both square pyramidal and trigonal bipyramidal geometries.
Keywords: Pyrazine tetrazolate (pzta); In situ; Hydrothermal; Framework;

Highly efficient chemical fixation of carbon dioxide catalyzed by high-valent tetraphenylporphyrinatotin(IV) triflate by Fatemeh Ahmadi; Shahram Tangestaninejad; Majid Moghadam; Valiollah Mirkhani; Iraj Mohammadpoor-Baltork; Ahmad Reza Khosropour (1489-1493).
High-valent tetraphenylporphyrinatotin(IV) triflate, [SnIV(TPP)(OTf)2], was found as an efficient catalyst for the coupling of several epoxides (linear and cyclic) with carbon dioxide in the presence of tetrabutylphosphonium bromide as co-catalyst at atmospheric pressure. The reaction temperature, kind of solvent, co-catalyst and axial ligand effect were also investigated.High-valent tetraphenylporphyrinatotin(IV) triflate, [SnIV(TPP)(OTf)2], was found as an efficient catalyst for the coupling of several epoxides (linear and cyclic) with carbon dioxide in the presence of tetrabutylphosphonium bromide as co-catalyst at atmospheric pressure. The reaction temperature, kind of solvent, co-catalyst and axial ligand effect were also investigated.Display Omitted► Electron-deficient tin(IV)porphyrin was used as catalyst. ► Cyclic carbonates were obtained by the reaction of CO2 with epoxides. ► The reaction was carried out at atmospheric pressure.
Keywords: CO2 fixation; [Sn(TPP)(OTf)2]; Epoxides; Cyclic carbonates; Co-catalyst;

5-Amino-iso-phthalic acid (AIPA) is modified with 3-(triethoxysilyl)-propyl isocyanate (TEPIC) to achieve special di-urea bridge (abbreviated as AIPASi) which behave as a linkage between Eu3+/Tb3+ and composite gels Si–O–M (M = Si, B, Ti) by controlling the hydrolysis rate of alkoxy compounds (tetraethyl orthosilicate (TEOS), titanium butoxide (TBT) and tributyl borate (TBB)). Subsequently, the Eu3+/Tb3+ covalently immobilized in AIPA functionalized composite gels are assembled and characterized and especially photoluminescent properties (luminescence spectroscopy, lifetimes and quantum efficiency) are discussed. The hybrids with composite Si–O–B gels possess the better photophysical properties than Si–O–Ti gels and even than pure silica gels.Three kinds of hybrid xerogel systems of rare earth ions (Eu3+, Tb3+) with 5-amino-iso-phthalic acid functionalized linkage AIPASi have been assembled through coordination bonds and show the photoluminescence property.Display Omitted► Composite gel of Si–O–M (M = B, Ti). ► Hybrids with Si–O–B possess favorable luminescence property. ► Sol–gel process of different alkoxides.
Keywords: Photofunctional hybrid gel; Lanthanide ion; Luminescence; Sol–gel preparation; Composite host;

Spin crossover polymeric iron(II) complex based on triazole with branched long alkyl chain by Young Hoon Lee; Yasuka Komatsu; Yuuki Yamamoto; Kazuya Kato; Tetsuya Shimizu; Asuka Ohta; Takeshi Matsui; Shinya Hayami (1498-1500).
Novel 1-D polymeric metallo-organic triazole iron(II) complex {[Fe(C5C12C10-trz)3](ClO4)2}n (1) with branched long alkyl chain was synthesized and characterized in detail. The compound exhibited liquid crystal transition and spin crossover behavior. The liquid crystal transition occurred at 233 K, and the spin crossover was observed at T1/2↑ = 250 K and T1/2↓ = 248 K.Novel 1-D polymeric metallo-organic triazole iron(II) complex{[Fe(C5C12C10-trz)3](ClO4)2}n with branched long alkyl chain was synthesized. The compound exhibited liquid crystal transition and spin crossover behavior. The liquid crystal transition occurred at 233 K, and the spin crossover was observed at T1/2↑ = 250 K and T1/2↓ = 248 K.Display Omitted► Novel 1-D polymeric triazole iron(II) complex with branched long alkyl chain was synthesized. ► The compound exhibited liquid crystal transition and abrupt spin crossover behavior. ► The liquid crystal transition occurred at 233 K.
Keywords: Spin crossover; Branched long alkyl chain; Polymeric iron(II) complex; Phase transition;

( EnH2)2[V2O2(O2)4(μ-C2O4)] — The vanadium(V) oxalato oxido peroxido complex with a bridging oxalato group by Mária Grešnerová; Jana Chrappová; Peter Schwendt; Jozef Tatiersky; Zdirad Žák (1501-1503).
The oxalato complex (EnH2)2[V2O2(O2)4(μ-C2O4)] (where En = ethane-1,2-diamine) has been prepared and characterised by elemental analysis, infrared and Raman spectra and single crystal X-ray analysis. The crystal structure is stabilised by an extensive network of simple, bi-, tri- or tetrafurcated N―H···O hydrogen bonds which is supposed to have a significant role in stabilising the dinuclear solid state structure of the [V2O2(O2)4(μ-C2O4)]4− anion. The 51V NMR spectrum showed that the dinuclear complex is decomposing immediately after its dissolution in water.The choice of a proper counter cation facilitated the preparation of the first peroxidovanadium complex with bridging oxalato(2−) group.Display Omitted► Synthesis of novel peroxidovanadium complex with μ-η22 oxalato group. ► X-ray structure analysis. ► IR, Raman and NMR spectra.
Keywords: Vanadium(V) complex; Oxalato ligand; Peroxido ligand; NMR; X-ray structure;

New cadmium-promoted reaction of a C-nucleophile: Synthesis and X-ray structure of the first dicyanopyrazine iron(II) clathrochelate by Oleg A. Varzatskii; Yan Z. Voloshin; Pavel A. Stuzhin; Sergey V. Shul'ga; Sergey V. Volkov; Anna V. Vologzhanina; Ekaterina G. Lebed; Yurii N. Bubnov (1504-1507).
The first macrobicyclic complex with pendant ribbed dicyanopyrazine substituent was obtained by the new carbanion condensation of the clathrochelate precursor FeBd2(Cl2Gm)(BF)2 (where Bd2– and Cl2Gm2– are α-benzyldioximate and dichloroglyoxime dianions, respectively) with 2,3-dicyano-5,6-dimethylpyrazine in the presence of the cadmium(II) amide as a promoter at r.t. Only one pair of the carbanionic and electrophilic reactive centers is involved in a condensation giving the monosubstituted clathrochelate, whereas the product of the double condensation of its vic-dihalogen-containing chelate fragment with ortho-dimethylsubstituted pyrazine molecule was not detected. This result is explained by the formation on the first stage of the intermediate dicyanopyrazine carbanion, which is stabilized by the coordination of its heterocyclic nitrogen atom to the cadmium(II) ion. The clathrochelate obtained has been characterized using elemental analysis, MALDI-TOF mass spectrometry, IR, UV–vis, 1H and 13C{1H} NMR spectroscopies, and X-ray diffraction crystallography. The clathrochelate synthesized demonstrates strong CH-acidity: in the presence of strong organic bases its color changes from yellow-brown to violet due to the formation of a clathrochelate anion with highly conjugated azapolyene π-system. Cadmium-promoted condensation is proposed as useful tool to perform other carbanionic reactions as well as to synthesize the functionalized electron-withdrawing heterocycles by alkylation and heteroarylation of their available reactive derivatives.The first macrobicyclic complex with pendant ribbed dicyanopyrazine substituent was obtained using novel cadmium-promoted carbanion condensation of the iron(II) dichloroclathrochelate precursor with 2,3-dicyano-5,6-dimethylpyrazine. Only one pair of the carbanionic and electrophilic reactive centers is involved in a condensation giving the monosubstituted clathrochelate product.Display Omitted► The iron(II) clathrochelate undergoes a nucleophilic substitution with C-nucleophile. ► Cadmium-promoted reaction with dimethyldicyanopyrazine yields C-alkylated macrobicycle. ► Carbanionic condensation of the iron(II) clathrochelate gave a monosubstituted complex. ► C-nucleophilic substitution is novel approach to functionalization of cage complexes.
Keywords: Macrocyclic compounds; Clathrochelates; Iron complexes; Nucleophilic substitution; Ligand reactivity;

Azide anion encapsulation in a tetraurea receptor by Xiaolei Wang; Chuandong Jia; Xiaojuan Huang; Biao Wu (1508-1510).
The azide complex [Na(15-crown-5)]2[L(N3)2] has been synthesized. X-ray single-crystal diffraction analysis revealed that two orthogonally oriented azide anions are encapsulated in one receptor, each by two opposite urea edges of the square tetreurea ligand through N(urea)  − H⋯N(azide) hydrogen bonding. UV–vis titration confirmed the 1:2 (host/guest) binding mode in solution with slight bathochromic shifts compared to the ligand.An azide complex [Na(15-crown-5)]2[L(N3)2] has been synthesized, in which two orthogonally oriented azide anions are encapsulated in one receptor, each by two opposite urea edges of the square tetraurea ligand L through N(urea)  − H⋯N(azide) hydrogen bonding.Display Omitted► A tetraurea anion receptor is used for the binding of azide anion. ► Two azide anions are encapsulated within one receptor forming a 1:2 host/guest complex. ► Each anion is bound by two alternate urea groups of the nearly square tetraurea ligand.
Keywords: Anion binding; Tetraurea receptors; Azide encapsulation; N(urea) ―H⋯N(azide) hydrogen bonding;

New 2-phenyl-5-nitropyridyl containing iridium(III) cyclometalated complexes: syntheses, structures, electrochemistry and photophysical properties by Xuan Shen; Feng-Ling Wang; Feng Sun; Rui Zhao; Xin Wang; Su Jing; Yan Xu; Dun-Ru Zhu (1511-1515).
A series of new 2-phenyl-5-nitropyridyl containing iridium(III) cyclometalated complexes ([Ir(5-NO2-ppy)2Cl]2 (1, 5-NO2-ppy = 2-phenyl-5-nitropyridyl), Ir(5-NO2-ppy)2(PPh3)Cl (2, PPh3  = triphenylphosphine), Ir(5-NO2-ppy)2(pic) (3, pic = picolinic acid)) have been synthesized and unambiguously characterized. The crystal structures of 2 and 3 have been determined by X-ray diffraction analyses. The HOMO–LUMO energy gaps of 13 estimated by the cyclic voltammetry (CV) show values in the order of 2  >  3  >  1. The UV–vis absorption and the solid photoluminescence (PL) spectra of 13 have also been measured, exhibiting the changing orders being consistent with that of the HOMO–LUMO energy gaps. Moreover, the UV–vis absorption spectra of 13 show obvious red-shifts compared with those of the corresponding 2-phenylpyridyl (ppy) containing Ir(III) complexes ([Ir(ppy)2Cl]2, Ir(ppy)2(PPh3)Cl and Ir(ppy)2(pic)) in which no strongly electron-withdrawing nitro groups are introduced to the pyridyl rings of the ppy ligands. Thus, the HOMO–LUMO energy gaps of 13 should be narrower than those of [Ir(ppy)2Cl]2, Ir(ppy)2(PPh3)Cl and Ir(ppy)2(pic).A series of new iridium(III) complexes ([Ir(5-NO2-ppy)2Cl]2 (1, 5-NO2-ppy = 2-phenyl-5-nitropyridyl), Ir(5-NO2-ppy)2(PPh3)Cl (2) and Ir(5-NO2-ppy)2(pic) (3)) in which the strongly electron-withdrawing nitro groups are introduced to the pyridyl rings of the 2-phenylpyridyl (ppy) ligands have been synthesized and characterized, showing narrower HOMO–LOMO energy gaps compared with the corresponding ppy containing complexes.Display Omitted► A series of 2-phenyl-5-nitropyridyl containing iridium(III) complexes are presented. ► Electron-withdrawing nitro groups are introduced to the pyridyl of the complexes. ► The crystal structures of two new Ir(III) complexes are determined. ► Electrochemistry and photophysical properties of the complexes are investigated. ► These new Ir(III) complexes show narrow HOMO–LUMO energy gaps.
Keywords: 2-Phenyl-5-nitropyridyl; Iridium(III) complex; Crystal structure; HOMO–LUMO energy gap; Red-shift; Electron-withdrawing group;

Synthesis and photochemical properties of cationic cyclopentadienyliron containing arylazo chromophores by Guang-Lei Li; Hui Ye; Yu Chen; Bao-Dong Zhao; Tao Wang (1516-1519).
Two kinds of cationic cyclopentadienyliron complexes containing arylazo chromophores (Azo-Fc) were synthesized through the nucleophilic aromatic substitution reactions of cyclopentadienyliron chlorobenzene complexes. The synthesized Azo-Fc was characterized by LC–MS, IR, and 1H NMR. The influence of substituents and the aryl ring on spectral data of the synthesized compounds is described. Unlike other cationic cyclopentadienyliron complexes, Azo-Fc hardly underwent photolysis and showed no photo-initiating abilities in the cationic polymerization under photo-irradiation; in addition, trans/cis isomerization by irradiation is possible at different wavelengths.Two kinds of cationic cyclopentadienyliron complexes containing arylazo chromophores which can undergo trans/cis isomerization by irradiation at different wavelengths were investigated.Display Omitted► Six new cationic cyclopentadienyliron complexes containing arylazo chromophores (Azo-Fc) were synthesized. ► UV–vis results showed that Azo-Fcs have strong absorption in the regions 300–450 nm. ► Unlike other cationic cyclopentadienyliron complexes, Azo-Fcs cannot undergo photolysis under a halogen lamp. ► Azo-Fcs can undergo reversible trans/cis isomerization by irradiation at different wavelengths.
Keywords: Cationic cyclopentadienyliron complex; Synthesis; Photochemistry; Trans/cis isomerization;

Synthesis, crystal structure, photophysical property and electropolymerization of Pt(II) complexes with carbazole-grafting 2-(2-pyridyl)benzimidazole by Dongfang Qiu; Yingchen Guo; Hongwei Wang; Xiaoyu Bao; Yuquan Feng; Qunzeng Huang; Junliang Zeng; Guozeng Qiu (1520-1524).
Two neutral-charged Pt(II) complexes, i.e., [(PBC)PtCl2] (5) and [(PBC)Pt(C ≡ CC6H5)2] (6) (PBC = N-[4-(9-carbazole)butyl]-2-(2-pyridyl)benzimidazole) have been synthesized and verified by 1H NMR and X-ray crystallography. In each of them, the coordinate geometry of Pt atom is a distorted square planar configuration with bond distances and angles in the normal range. Complex 6 shows an intense metal-to-ligand charge transfer (1MLCT) ((Pt) →  π*(L)) transition at 412 nm in the UV-Vis absorption spectrum and a strong phosphorescence at 593 nm in CH2Cl2 solution at ambient temperature. By selective optical-stimulation at 320 nm, an incomplete intramolecular energy transfer process from the carbazole unit to the [(PB)Pt(C ≡ CC6H5)2] center results in unbalanced dual-emissive bands of a quenched carbazole-based luminescence in deep blue region and an orange 3MLCT emission with increasing intensity. The introduction of carbazole unit also triggers the electropolymerization of ligand PBC and complexes 5 and 6. The as-formed polymer film from complex 5 has good conductivity, stability and clear anodic coloration effect.Functionalized Pt(II) complexes: The neutral-charged Pt(II) arylacetylide and chloride complexes with N-[4-(9-carbazole)butyl]-2-(2-pyridyl)benzimidazole (PBC) show an enhanced orange 3MLCT emission induced by an intramolecular energy transfer process and the promising electropolymerization activity to form an anodic coloration film, respectively.Display Omitted► Carbazole unit as the high triplet energy donor. ► Bi-chromophoric system with an intramolecular energy transfer process. ► Carbazole unit as the electro-active moiety. ► Conductive metallopolymer film with a clearly electrochromic behaviour.
Keywords: Pt(II) complex; Carbazole; 2-(2-pyridyl)benzimidazole; Crystal structure; Photophysics; Electropolymerization;

The microwave-assisted solvothermal synthesis (180 °C, 1 h) of a mixture of neodymium chloride, 1-10-phenanthroline (phen) in ethanol gives rise to the crystallization of a new phase, NdCl3(H2O)(phen). Its crystal structure consists of eight-fold coordinated lanthanide atoms, (bicapped trigonal prism, NdN2Cl5(H2O)) linked to each other through μ 2-chloro groups via edge-sharing connection mode in order to generate infinite ribbons. The cohesion of the three-dimensional structure is ensured through hydrogen bond interactions between terminal chloride and water groups from distinct chains, as well as ππ interactions between the central benzene ring of two phen ligands. The occurrence of such a chain-like compound, with Nd/phen ratio of 1, is unique in the series of lanthanide-phenanthroline complexes. This compound is obtained by using a microwave heating procedure, which selectively induces the formation of such 1D coordination polymer. Thermogravimetric and infrared analyses are also detailed.Microwave-assisted solvothermal reaction of 1,10-phenanthroline with neodymium trichloride gave rise to the formation of a chain-like structural assembly containing eightfold coordinated metal NdCl3(H2O)(phen). This one-dimensional arrangement is specifically obtained by means of microwave heating instead of a discrete mononuclear motif by conventional heating.Display Omitted► Microwave-assisted solvothermal synthesis. ► Reactivity of 1,10-phenanthroline with neodymium trichloride. ► Infinite chain of eightfold coordinated neodymium through μ 2-Cl bridge. ► Phase selectivity microwave versus conventional heating.
Keywords: 1D coordination polymer; Lanthanide chloride; 1,10-phenanthroline; Microwave solvothermal synthesis; Single-crystal; X-ray diffraction; Thermogravimetric analysis;

Unique tetranuclear heterometallic compound [Na2Zn2{(4-py)C(H)(NOH)}2(CH3COO)6(H2O)4].2H2O with luminescent properties by Eduard B. Coropceanu; Lilia Croitor; Anatolii V. Siminel; Marina S. Fonari (1528-1531).
The luminescent heterometallic material, [Na2Zn2{(4-py)C(H)NOH}2(CH3COO)6(H2O)4].2H2O (1), where (4-py)C(H)NOH = pyridine-4-carbaldehyde oxime, was synthesized and characterized by single crystal X-ray method. In the centrosymmetric tetranuclear molecule each sodium site is bound to six oxygen atoms, the donor atoms come from three acetate anions and three water molecules, two of which act as μ2-aqua bridges between Na(I) centers. Each zinc site is bound to three oxygen atoms from the same acetate anions and one nitrogen atom from the capped (4-py)C(H)NOH molecule which coordinates via pyridine nitrogen. The bridging acetate ligands show two coordination modes within one compound.The unprecedented heterometallic tetranuclear compound [Na2Zn2{(4-py)C(H)NOH}2(CH3COO)6(H2O)4].2H2O, where (4-py)C(H)NOH = pyridine-4-carbaldehyde oxime was synthesized and characterized by single crystal X-ray method. The acetate anions and water molecules bridge the metal centers. The capped (4-py)C(H)NOH molecules coordinate to the terminal Zn(II) atoms via pyridine nitrogens. The new material reveals strong luminescent properties.Display Omitted► Synthesis and X-ray structural study of tetranuclear heterometallic Zn-Na cluster. ► Two bridging coordination modes of acetate anion were registered in one compound. ► The compound exhibits luminescence emission.
Keywords: Heterometallic cluster; Zinc; Structure; Luminescence;

A new 3D lanthanide metal–organic framework, {[Ce(L)(DMF)]·2.5(DMF)·3(H2O)}n (1) (H3L = N,N′,N″-tris(4-carboxyphenyl)-1,3,5-benzenetricarboxamide, DMF = N,N′-dimethylformamide) has been synthesized under solvothermal condition. Compound 1 features a 3D non-interpenetrated binodal (4, 8)-connected AlB2 topology with a Schläfli symbol of (45.6)2(410.614.84), where the C 3 symmetry ligand H3L evolves into an unusual 4-connected node and dinuclear cerium cluster acts as an 8-connected node. Furthermore, compound 1 displays blue emission in the solid state at room temperature.A 3D metal–organic framework {[Ce(L)(DMF)]·2.5(DMF)·3(H2O)}n, featuring unusual binodal (4, 8)-connected AlB2 topology, has been synthesized, in which the C 3 symmetry H3L evolves into an 4-connected node and dinuclear cerium cluster acts as an 8-connected node.Display Omitted► The first lanthanide MOF with (4, 8)-connected AlB2 topology has been synthesized by C 3 symmetry H3L ligand, which evolves into an unusual 4-connected node due to the coordination of one carbonyl-oxygen atom from amide group. ► The structure transition between (4, 8)-connected AlB2 and (3, 6)-connected rutile networks based on H3L ligand is studied. The luminescent properties are investigated.
Keywords: Metal–organic frameworks; AlB2 topology; Lanthanide; C 3 symmetry ligand;

Solvothermal reactions of Cu2(OH)2CO3 with 1,2-bis(4-pyridyl)ethane (bpe) and iodobenzene or 4-iodotoluene in acetonitrile and aqueous ammonia afforded two arylamine-solvated [Cu2I2]-based coordination polymers {[Cu2I2(bpe)2]∙Am} n (1: Am = aniline; 2: Am =  p-toluidine). Compounds 1 and 2 were characterized by elemental analysis, IR spectra, and powder X-ray diffraction (PXRD). Compounds 1 and 2 have a two-dimensional (4,4) topological network in which every rhombic [Cu2I2] dimer acts as a planar four-connected node to link other four equivalent ones by four bpe bridges. Each layer is further stacked via ππ interactions to form a 3D structure with 1D rhombic channels occupied by the guest aniline or p-toluidine molecules. These guest molecules were in situ generated through Ullmann coupling reactions of iodobenzene or 4-iodotoluene with ammonia. The thermal and photoluminescent properties of 1 and 2 were also investigated.Two arylamine-solvated [Cu2I2]-based coordination polymers {[Cu2I2(bpe)2]∙Am} n (1: Am = aniline; 2: Am =  p-toluidine) were generated from solvothermal reactions of Cu2(OH)2CO3 with 1,2-bis(4-pyridyl)ethane (bpe) and iodobenzene or 4-iodotoluene in MeCN and aqueous ammonia. Both complexes were structurally characterized by elemental analysis, IR, and X-ray crystallography and their thermal and luminescent properties were studied.Display Omitted► Reaction of Cu2(OH)2CO3 with bpe and PhI in MeCN and aqueous NH3 gave compound 1. ► Compound 1 has a [Cu2I2]-based 2D (4,4) topological network. ► The aniline molecule was in situ formed through Ullmann reactions of PhI with NH3.
Keywords: Copper(I); 1,2-Bis(4-pyridyl)ethane; Solvothermal reaction; Coordination polymer; Iodide; Amination;

A series of Ni6-substituted polyoxometalates derivated from tripodal alcohol ligands by Xin-Xiong Li; Shou-Tian Zheng; Wei-Hui Fang; Guo-Yu Yang (1541-1545).
A series of new polyoxometalates based on [Ni63-OH)3(H2O)6(en)3(B-α-PW9O34)] (en = ethylenediamine) clusters capped by different tripodal alcohol ligands have been hydrothermally synthesized and characterized by IR, TGA and single-crystal X-ray diffraction, respectively. The experimental results indicate that the tripodal alcohol ligands can substitute three hydroxyl groups located on the axial positions of the Ni6 cluster to form new polyoxometalates with different substituted modes.Four new polyoxometalates based on [Ni63-OH)3(H2O)6(en)3(B-α-PW9O34)] (en = ethylenediamine) units have been hydrothermally synthesized and structural characterized, in which the tripodal alcohol ligands can substitute three hydroxyl groups located on the axial positions of the Ni6 cluster to form new polyoxometalates with different substituted modes.Display Omitted► Three-dimensional organic–inorganic hybrid polyoxometalates (POMs). ► The axial OH groups of the Ni6 core can be replaced. ► The substituted POMs decorated by flexible tripodal alcohol ligands (TALs). ► The introduction of the TALs provides new potential for the structure expansion.
Keywords: Hydrothermal synthesis; Polyoxometalates; Nickel; Keggin; Tripodal alcohol ligand;

A glycine ligand coordinated hybrid complex constructed from hexanuclear copper clusters and octamolybdates by Xiao-Yu Jiang; Xiao-Yuan Wu; Rong-Min Yu; Da-Qiang Yuan; Wen-Zhe Chen (1546-1549).
Self-assembly of the sodium molybdate, copper chloride and glycine in aqueous solution results in a novel compound, {[NaCu6(Gly)8(H2O)2][Mo8O26(GlyH)2(Cu(Gly)H2O)]2}{NaCu6(Gly)8(H2O)2}{Mo8O26(GlyH)2}·16H2O (1). Compound 1 contains a new unit of {[NaCu6(Gly)8(H2O)2][Mo8O26Cu(Gly)2]2}, in which the [Mo8O26Cu(Gly)2] polyoxometalate units are connected by the [NaCu6(Gly)8(H2O)2] hexanuclear copper cluster. The magnetic measurement of 1 shows that ferromagnetic coupling exists between the magnetic centers of the hexanuclear copper cluster.A new POM/amino acid hybrid compound has been synthesized. The coordination complex contains a new unit of {[NaCu6(Gly)8(H2O)2][Mo8O26Cu(Gly)2]2}, in which two [Mo8O26Cu(Gly)2] polyoxometalate units are connected by the [NaCu6(Gly)8(H2O)2] hexanuclear copper cluster.Display Omitted► A novel compound contains hexanuclear copper cluster and octamolybdate cluster. ► The two types of clusters are combined by amino acid ligand. ► It is the first example of discrete structure with high-nuclear Na–Cu cluster as node.
Keywords: Hybrid material; Polyoxometalate; Hexanuclear copper cluster; Amino acid; Magnetic properties;

In this study Benzenesulfonicacid-1-methylhydrazide (bsmh) derivatives such as salicylaldehyde benzenesulfonylhydrazone (Hsalbsmh) and its Ni(II), Pd(II), Pt(II), Cu(II), Co(II) complexes were synthesized for the first time. The structure of these complexes was investigated by using elemental analyses, the FT-IR, LC–MS and UV–VIS spectrophotometric methods, magnetic susceptibility and conductivity measurement techniques. The complexes were found to have general compositions [ML2]. Using disk diffusion methods all the synthesized complexes were evaluated in vitro as antimicrobial agents against representative strains of gram-positive (Staphylococcus aureus ATCC 25923, Bacillus cereus ATCC 11778, Enterococcus faecalis ATCC 29212, Bacillus subtilis ATCC 6633, Staphylococcus epidermidis ATCC 12228, Enterobacter aerogenes ATCC 13048) and gram-negative bacteria (Pseudomonas fluorescens ATCC 49838, Klebsiella pneumoniae ATCC 13883, Escherichia coli ATCC 25922, Pseudomonas aeruginosa ATCC 27853) and as an antifungal agent against Candida albicans (ATCC 90028). All the bacteria and fungus studied were screened against some antibiotics to compare with our chemical zone diameters.We obtained a new ligand (Hsalbsmh) and its five metal complexes [Ni(salbsmh)2, Pd(salbsmh)2, Pt(salbsmh)2, Cu(salbsmh)2 and Co(salbsmh)2] and characterized their structure by FT-IR, Elemental Analysis, UV–VIS, Magnetic Susceptibility and LC/MS techniques and investigated their antibacterial activities.Display Omitted► Benzenesulfonicacid-1-methylhydrazide (bsmh) + Salycylaldehyde → salycylaldehyde benzenesulfonylhydrazone (Hsalbsmh). ► Hsalbsmh  +  MCl 2  → M(salbsmh)2 (M: Ni(II), Pd(II), Pt(II), Cu(II), Co(II)). ► Characterization Hsalbsmh and its complexes. ► Antimicrobial activities of Hsalbsmh and its complexes.
Keywords: Antimicrobial activity; Sulfonamides; Aromatic sulfonamide; Sulfonamide complexes;