Inorganic Chemistry Communications (v.45, #C)

Contents List (iii-xi).

Ligand configuration introduced into a 3D self-interpenetrated coordination polymer as visible-light-driven photocatalyst by Xiao Wang; Quan-Guo Zhai; Xiang-Yang Hou; Shu-Ni Li; Yu-Cheng Jiang; Man-Cheng Hu (1-4).
The combination of 1,4-bis(imidazol-1-ylmethyl)benzene (BIYB) and anthraquinone-2,7-disulfonic acid (H2AQDA) ligands leads to a copper coordination polymer, namely, {[Cu(BIYB)2(AQDA)]·H2O} n (1). The cis-BIYB ligands link one unique Cu(II) atoms to give 1D double chains, but trans-BIYB connects the other Cu(II) centers to generate 2D (4,4)-layers. Each H2AQDA ligand acts as a μ2-bridging linking the double chains and (4,4)-layers to generate the 3D framework of 1. Cu(1) and Cu(2) can be viewed as 6- and 4-connected nodes, which lead to a (4,6)-connected self-penetrated network. Notably, complex 1 represents the rare example of coordination polymer-based visible-light-driven photocatalyst, and shows good degradation efficiency of organic dye.A unique 3D interpenetrated Cu coordination polymer framework triggered by the cis- and trans-configurations of organic ligand exhibits remarkable visible-light-driven photocatalytic activity.Display Omitted
Keywords: Coordination polymer; Ligand configuration; Interpenetration; Photocatalyst;

A novel mononuclear metal–organic compound, N-chloromethyl-1,4-diazabicyclo-[2.2.2]octonium trichlorobromoaquo copper(II), Cu(LCH2Cl) (H2O) Br2.75Cl0.25 (1) (L + CH2Cl = N-chloromethyl-1,4-diazabicyclo[2.2.2]octonium ion) was synthesized. Differential scanning calorimetry (DSC) results showed that this compound underwent a reversible phase transition at ca. 190 K with a hysteresis of 11 K width and single crystal X-ray diffraction data suggested that there was a transition from a room-temperature phase with the space group of Pnma (a = 17.790(2) Å, b = 9.0000(12) Å, c = 8.2263(11)Å, V = 1317.1(3) Å3 and Z = 1) to a low-temperature one with the space group of P21/n (a = 8.184(4) Å, b = 17.681(8) Å, c = 8.941(4) Å, β = 91.218(6)°, V = 1293.5(10) Å3 and Z = 1). Symmetry breaking occurred with the Aizu notation of mmmF2/m. The ordering of twisting motions of 1,4-diazoniabicylo[2,2,2]octane ring may drive the phase transition.A novel compound, Cu(LCH2CI) (H2O) Br2.75 Cl0.25 (1) was synthesized. The single crystal X-ray diffraction data suggests that the phase transition undergoes from a room temperature phase with a space group of Pnma to a low temperature one with a space group of P21/n.Display Omitted
Keywords: Cu(II) compound; Phase transition; Symmetry breaking; Variable-temperature X-ray;

Schiff base bridged biporphyrin: Synthesis, characterization and spectral properties by Ya Hong Wu; Ling Ling Hu; Jing Zhang; Jian Yu; Shan Ling Tong; Yan Yan (10-14).
Chromophoric molecules with mono-aminophenyl, 5-aminophenyl-10, 15, 20-triphenyl porphyrin, were chemically reduced from the precursors of 5-nitrophenyl-10, 15, 20-triphenyl porphyrin. The titled Schiff base bridged biporphyrins were furthermore prepared by condensation of 5-aminophenyl-10, 15, 20-triphenyl porphyrin with terephthalaldehyde. This novel conjugated Schiff base biporphyrin was well characterized by spectral determinations. Experimental results indicated that the titled compound possessed fluorescence enhancement in near infrared region. Compared with tetraphenyl porphyrin, both ultraviolet–visible absorption and fluorescence spectra of the titled compound appeared with slightly red shift. Photo experiments revealed that, after violet irradiation, the color of a chloroform solution with the titled compound changed sharply from pale green to dark green along with sensitively spectral variation during ultraviolet–visible absorption and electron paramagnetic resonance determinations. This sensitively photochromic mechanism was well explained by molecular recognition of the titled compound towards hydrogen chloride from the decomposition of the chloroform solvent. The titled compound was sensitive in recognizing towards hydrogen chloride.A Schiff base bridged biporphyrin was synthesized by condensation of p-aminophenyl-triphenylporphyrin with terephthalaldehyde. The target product was characterized carefully by spectral method and furthermore its molecular recognition towards hydrogen chloride was well described.Display Omitted
Keywords: Schiff base; Porphyrin; Molecular recognition; Molecular wire; Halochromism; Photochromism;

The selective assay of Al3 + and Zn2 + ions is reported using fluorescence enhancement of a simple Schiff base receptor 1 (1  = 1-((E)-(1,3-dihydroxy-2-(hydroxymethyl)propan-2-ylimino)methyl)naphthalen-2-ol) in aqueous solvents. The Schiff base receptor 1 showed a turn-on fluorescence in the presence of Al3 + in a mixture of methanol–water, as a result of a restricted C=N isomerization mechanism. The ion selectivity of 1 could be switched for Zn2 + by swapping the solvent from methanol–water to DMF–water mixture. In particular, this chemosensor could clearly distinguish Zn2 + from Cd2 +. The binding properties of 1 with the metal ions were investigated by UV–vis, fluorescence, electrospray ionization mass spectroscopy and 1H NMR titration.The selective assay of Al3 + and Zn2 + ions is reported using fluorescence enhancement of a simple Schiff base receptor 1 in aqueous solvents. The receptor 1 showed a turn-on fluorescence in the presence of Al3 + in a mixture of methanol–water, as a result of a restricted C=N isomerization mechanism. The ion selectivity of 1 could be switched for Zn2 + by swapping the solvent from methanol–water to DMF–water mixture.Display Omitted
Keywords: Al3 +; Zn2 +; Schiff base; Fluorescent chemosensor; C=N isomerization;

Two 2D grid-based Co(II) amino acid Schiff base complexes with left- and right-handed helical chains: Structures and magnetism by Zong-Ze Li; Lin Du; Xue-Zhong Zhang; Zhu-Li Li; Lin Li; Jing Yang; Qi-Hua Zhao (20-24).
Two layered Co(II) amino acid Schiff base complexes, [Co(napala)(tbpe)0.5]n (1) and [Co(napgly)(tbpe)0.5]n (2) [H2napala =  N-(2-hydroxy-1-naphthylmethylidene)-d/l-alanine, H2napgly =  N-(2-hydroxy-1-naphthylmethylidene)-glycine and tbpe =  trans-1,2-bis(4-pyridyl)ethylene], have been synthesized by solvothermal methods and characterized using single-crystal X-ray diffraction. The bridging of Schiff base ligands napala2 − or napgly2 − with Co(II) forms one-dimensional (1D) left- and right-handed helical chains which are further pillared by tbpe to build a two-dimensional (2D) grid-based hcb-type framework. Moreover, both complexes show high thermal stability and exhibit antiferromagnetic coupling between the Co(II) centers mediated by the synanti-COO-bridges.Two new Co(II) amino acid Schiff base complexes exhibit 2D grid-based layers. The 2D structures contain left- and right-handed helical chains and trans-1,2-bis(4-pyridyl)ethylene bridges. The magnetic properties of the complexes were studied in details.Display Omitted
Keywords: Schiff base; Cobalt; Helical chain; 2D framework; Antiferromagnetism;

A new 3d–4f heterometallic coordination polymer [Gd(H2O)3(NO3 )(CuL)2] •H2O (1) (H3L = glycylglycine, N-[1-(2-hydroxy, phenyl)-propylidene]) has been synthesized and characterized by IR, elemental analysis, TGA and X-ray single-crystal diffraction. In the coordination polymer, two metallo-ligand CuLs are connected with Gd3 + ion to form a 1-D chain via carboxylate and carbonyl oxygen. The neighboring Cu–Gd–Cu chains are further connected by hydrogen bonds to form a two-dimensional structure. Magnetic studies for 1 reveal that ferromagnetic interactions (J CuGd  = 1.30 cm− 1) between Cu(II) and Gd(III) centers are operating within the CuII–GdIII–CuII systems.A new 3d–4f heterometallic coordination polymer [Gd(H2O)3(NO3 )(CuL)2] •H2O (1) (H3L = glycylglycine, N-[1-(2-hydroxy, phenyl)-propylidene]) has been synthesized and structurally characterized by X-ray single-crystal diffraction. Magnetic studies for 1 reveal that ferromagnetic interactions (J CuGd  = 1.30 cm− 1) between Cu(II) and Gd(III) centers are operating within the CuII–GdIII–CuII systems.Display Omitted
Keywords: Coordination polymer; Metallo-ligand; Dipeptide Schiff base; Crystal structure; Magnetic property;

A new acylamide MOF showing uncommon ten-fold interpenetration by Li-long Dang; Jian-qiang Li; Shu-juan Liu; Ming-biao Luo; Feng Luo (30-32).
In this work, we obtained a novel three-dimensional acylamide MOF, namely Zn(L) (BPDC)·H2O(1, BPDC2 −  = biphenyl-4,4′-dicarboxylate, L = N,N′-diphenyl-terephthalamide) by solvo(hydro)thermal method. This polymer was characterized by single-crystal X-ray diffraction, thermogravimetry and solid-state luminescence analysis. The outstanding structural feature of compound 1 is 4-connected dia net with uncommon 10-fold interpenetration in the [5 + 5] manner.We present here a 4-connected dia net with uncommon 10-fold interpenetration in the [5 + 5] mode, featuring 66 topology symbol. Moreover, the solid-state photoluminescence properties of polymer 1 are uncommon.Display Omitted
Keywords: MOFs; Solvo(hydro)thermal method; Dia net; 10-fold interpenetration;

A Ag―La coordination polymer of metatungstate (H2W12O40 6 −) and 2-pyrazinecarboxylic acid (L), (H3O)[Ag6La(H2O)6L4(H2W12O40)](1), was synthesized hydrothermally and characterized by elemental analysis, IR spectroscopy, and thermal gravimetric analysis. Single-crystal X-ray analysis reveals that the compound 1 crystallizes in monoclinic system with C2/c space group. In 1 Ag ions are coordinated by H2W12O40 6 − and 2-pyrazinecarboxylic acid. The linkage of Ag and L creates a AgL polymeric chain extending along b-axis. H2W12O40 6 − acts as a thirteen-dentate ligand and coordinates to sixteen Ag+ ions of six AgL chains, leading to a three dimensional structure. La3 + ion accepts six carboxyl oxygen atoms of four AgL chains and two water molecules, exhibiting a nearly cube geometry. Photoluminescent emission peak of 1 is observed at 438 nm which is attributed to LMCT or MLCT transition.Ag―La coordination polymer of metatungstate (H2W12O40 6 −) and 2-pyrazinecarboxylic acid (L), (H3O)[Ag6La(H2O)6L4(H2W12O40)](1), was synthesized hydrothermally and has a covalent 3D framework. H2W12O40 6 − shows the highest dentate number of a POM ligand.Display Omitted
Keywords: La―Ag coordination polymer; Metatungstate; Photoluminescence; Crystal structure;

Two new copper(II) complexes [Cu2L2(CH3OH)]·CH3OH (1) and [CuL]n (2) (H2L = N-(1-phenyl-3-methyl-4-benzal-pyrazolone-5)-salicylidene hydrazide) with different structures have been synthesized by the reactions of copper acetate with the 4-acyl pyrazolone derivative H2L in MeOH or EtOH solvent, respectively. The X-ray diffraction analyses revealed that 1 displays a dinuclear structure which is further linked by weak coordination interactions and hydrogen bonds to generate an infinite 1D chain. Complex 2 exhibits 1D left-handed and right-handed helical chains structure in a 1:1 ratio along the c axis, and the 1D chains with the same handedness were linked by hydrogen bonds to form a racemic two-fold interpenetrated 3D framework. The results demonstrated that the solvents with different coordination abilities have significant effect on the structure of the complexes. On the other hand, the ligands H2L adopt tridentate chelating mode and tetradentate chelating-bridging mode to coordinate with Cu(II) ions in 1 and 2, which attested that the flexible 4-acyl pyrazolone Schiff base derivative can adopt different coordination modes to form complexes with varied structures. The variable temperature magnetic investigation indicates that 2 exhibits typical antiferromagnetic behavior.Two solvent-induced complexes [Cu2L2(CH3OH)]·CH3OH (1) and [CuL]n (2) with dinuclear or 1D helical chain structures have been synthesized. The ligand can adopt tridentate chelating and tetradentate chelating-bridging modes to coordinate with Cu(II) ions. Complex 2 exhibits typical antiferromagnetic behavior.Display Omitted
Keywords: Copper(II); Solvent-induced effect; Crystal structure; Magnetic property;

A carbohydrazone based tetranuclear Co(II) complex: Self-assembly and magnetic property by Jing Li; Li Zhang; Guan-Cheng Xu; Wan-Xue Yu; Dian-Zeng Jia (40-43).
A tetranuclear cobalt(ΙΙ) complex [Co(HLMe,Me)]4(ClO4)4·5CH3OH·1.5H2O (H2LMe,Me  = 1,5-bis(1-(6-methylpyridine-2-yl)ethylidene)carbonohydrazide) was achieved by self-assembly and characterized by X-ray crystallographic analysis and magnetic measurement. In the Co4 rectangle grid, the Co(ΙΙ) centers are in a distorted octahedral environment with N4O2 or N5O coordination spheres and bridged by two μ-O bridges and two μ-N–N bridges, respectively. Variation in R2 site of the ligand influences the electromagnetic environment of the metal centers to some extent. The magnetic investigation indicates that there is an antiferromagnetic interaction between the HS Co(II) ions.A tetranuclear cobalt(ΙΙ) complex [Co(HLMe,Me)]4(ClO4)4·5CH3OH·1.5H2O with rectangle grid structure was self-assembled by a new carbohydrazone based ligand. Antiferromagnetic interaction between the HS Co(II) ions was found. Variation in R2 site of the ligand influences the electromagnetic environment of the metal centers to some extent.Display Omitted
Keywords: Co(ΙΙ) complex; Self-assembly; Tetranuclear; Carbohydrazone; Magnetism;

We have studied the metathetical reactions of cis-[PtCl2(TBZ)] (TBZ = 4-(1H-benzimidazol-2-yl)-1,3-thiazole) with two lead polyfluorobenzothiolates (Pb(SRF)2) giving rise to a complex equilibrium mixture of the monometallic platinum(II) compounds cis-[Pt(SRF)2(TBZ)] (SRF  = SC6F4(CF3)-4 (1), SC6HF4-4 (2)), the sulfur bridged bimetallic compounds cis-[Pt22-SRF)2(SRF)2(TBZ)2] (1a2a) and trans-[Pt22-SRF)2(SRF)2(TBZ)2] (1b2b), both exhibiting anti and syn isomers. We also report the X-ray diffraction crystal and molecular structures of the complexes cis-[PtCl2(TBZ)] (0), cis-[Pt(SC6F4(CF3)-4)2(TBZ)] 1 and trans-anti-[Pt22-SC6HF4-4)2(SC6HF4-4)2(TBZ)2] (2b). The platinum center in 0, 1 and 2b exhibits an almost perfect square planar coordination: Cl―Pt―Cl (89.47(6)°), S―Pt―S (94.82(13)°) and S―Pt―S (89.81(4)° and 83.41(4)°) respectively, 2b exhibits a planar [Pt2(μ-S)2] ring with the sulfur substituents in an anti configuration. cis-[Pt(SRF)2(TBZ)] (RF  = C6F4(CF3)-4 (1) and SC6HF4-4 (2) (TBZ = 4-(1H-benzimidazol-2-yl)-1,3-thiazole)) are in equilibrium with the sulfur bridged bimetallic compounds cis-[Pt22-SRF)2(SRF)2(TBZ)2] (1a2a) and trans-[Pt22-SRF)2(SRF)2(TBZ)2] (1b2b), both exhibiting anti and syn isomers. The X-ray diffraction molecular structures of the complexes cis-[PtCl2(TBZ)] (0), cis-[Pt(SC6F4(CF3)-4)2(TBZ)] (1) and trans-anti-[Pt22-SC6HF4-4)2(SC6HF4-4)2(TBZ)2] (2b) are reported.Display Omitted
Keywords: Platinum(II) polyfluorobenzothiolates; Crystal structure; Benzimidazol derivatives;

Synthesis and structure of [ReOSe(2-Se-py)3]: A rhenium(V) complex with selenium(0) as a ligand by Roberta Cargnelutti; Ernesto S. Lang; Paulo Piquini; Ulrich Abram (48-50).
Bis(2-pyridyl) diselenide (2-py2Se2, 1) reacts with [ReOCl3(PPh3)2] under the formation of the unusual oxidorhenium(V) complex [ReOSe(2-pySe)3], which was isolated in crystalline form and studied by spectroscopic methods and X-ray diffraction. The oxidorhenium(V) core is bonded to three 2-pyridineselenolato ligands together with a selenium(0) atom. While the rhenium atom is coordinated in a common distorted octahedral coordination sphere, the selenium(0) atom shows a bent T-shaped coordination with Se―N bonds of 2.13 (1) and 2.28 (1) Å and a Se―Re bond of 2.387 (1) Å. The oxidation state of the Se(0) atom has been analyzed using calculated atomic charges and the electron localization function (ELF).Bis(2-pyridyl) diselenide reacts with [ReOCl3(PPh3)2] under the formation of the unusual oxidorhenium(V) complex [ReOSe(2-pySe)3] having a Se(0) atom as ligand. The product was studied by spectroscopic methods, X-ray diffraction and DFT methods.Display Omitted
Keywords: Rhenium; Selenium; 2-Pyridylselenolate; X-ray structure; DFT calculations;

Synthesis and characterisation of the first examples of four-membered ring ruthenalactam complexes by Ashwin Gopalan Nair; William Henderson; Brian K. Nicholson (51-54).
Reaction of the complexes [RuCl2(PPh3)L] (L = η6-p-cymene or η6-hexamethylbenzene) with N-cyanoacetylurethane [NCCH2C(O)NHCO2Et] and tertiary amine base in refluxing methanol gives the first examples of mononuclear complexes containing the four-membered ruthenalactam ring, Ru–C–C(O)–N. The complexes were characterised by 1H and 31P{1H} NMR spectroscopy and ESI mass spectrometry. A single-crystal X-ray diffraction study on the p-cymene complex showed the four-membered ruthenalactam ring to be planar.The first examples of mononuclear complexes containing the four-membered ruthenalactam ring, Ru–C–C(O)–N, have been synthesised from [RuCl2(PPh3)L] (L = η6-p-cymene or η6-hexamethylbenzene) with N-cyanoacetylurethane [NCCH2C(O)NHCO2Et] and tertiary amine base in refluxing methanol; an X-ray diffraction study showed the four-membered ruthenalactam ring to be highly planar.Display Omitted
Keywords: Ruthenium; Metallalactam; Ruthenalactam; Electrospray ionisation mass spectrometry; Crystal structure;

Four new Cu(II), Ni(II), Co(II) and Zn(II) metalloinsertors have been synthesized by using a Schiff base, formed by the condensation reaction of 4-formyl-N,N-dimethylaniline with o-phenylenediamine. They have been structurally characterized by IR, NMR, UV–vis, EPR, elemental analyses, magnetic susceptibility and molar conductivity studies. The molar conductance data of the complexes indicate that they are non-electrolytes. The spectral and analytical data reveal that the complexes adopt square planar geometry. They have been examined for their antibacterial and antifungal activities against few pathogens. The data reveal that the complexes exhibit better biocidal activities against bacteria and fungi than the free Schiff base ligand. The interaction studies of these complexes with calf thymus deoxyribonucleic acid (CT DNA) have also been performed by using spectral, cyclic voltammetry and viscometry techniques which collectively give evidences for intercalative binding of DNA with metal complexes. The gel electrophoresis experiment reveals that the complexes are good chemical nucleases.The synthesized novel biologically active metal(II) complexes open the pledge of finding new clinically efficient antimicrobial compounds. They are good intercalators, laying the foundation for the ordinary design of new useful DNA probes and efficient inorganic metal complex nucleases.Display Omitted
Keywords: Metal complexes; Antibacterial activity; Antifungal activity; DNA binding; DNA cleavage;

Synthesis, spectroscopic studies and in vitro antibacterial activity of Ibuprofen and its derived metal complexes by Cristina Núñez; Adrián Fernández-Lodeiro; Javier Fernández-Lodeiro; Julia Carballo; José Luis Capelo; Carlos Lodeiro (61-65).
Complexes of Na+, Ag+, Ca2 +, Mg2 +, Cu2 +, Zn2 + and Hg2 + metal ions with the anti-inflammatory drug α-methyl-4-(2-methylpropyl)benzene acetic acid (Ibuprofen) have been synthesized and fully characterized. The IR spectroscopy data showed that Ibuprofen interacts with metal ions through the deprotonated carboxylate group in the bidentate form.Ibuprofen and its Ag+ and Hg2 + complexes showed antibacterial activity against the Gram-positive bacteria (Staphylococcus aureus and Listeria monocytogenes). The metal complexes resulted significantly more effective than the free Ibuprofen drug.Display Omitted
Keywords: Ibuprofen; Synthesis; Antibacterial; Mercury(II); Silver(I);

A novel series of [(dpca)MX2] (M = Cu, X = Cl; M = Cd, X = Br and M = Zn, X = NO3) complexes were synthesized through the reaction of N,N-di(2-picolyl)cyclohexylamine (dpca) with the corresponding metal starting materials. X-ray crystallographic analysis determined that the metal center in complexes [(dpca)CuCl2], [(dpca)CdBr2] and [(dpca)Zn(NO3)2] showed a distorted 5-coordinated square pyramidal, trigonal bipyramidal, and 7-coordinated pentagonal bipyramidal geometry, respectively, involving coordination of the nitrogen atom of the cyclohexylamine moiety with the metal center. Specifically, the catalytic activity of [(dpca)Zn(NO3)2] (1.04 × 105  g PMMA/mol Zn·h) for the polymerization of methyl methacrylate (MMA) in the presence of modified methylaluminoxane (MMAO) at 60 °C was six-fold higher than the reference complex [ZnCl2] (1.73 × 104  g PMMA/mol Zn·h).A novel series of complexes [(dpca)MX2] (M = Cu, X = Cl; M = Cd, X = Br and M = Zn, X = NO3) with N,N-di(2-picolyl)cyclohexylamine (dpca) were synthesized. A distorted 5-coordinated square pyramidal [(dpca)CuCl2], trigonal bipyramidal [(dpca)CdBr2], and 7-coordinated pentagonal bipyramidal [(dpca)Zn(NO3)2] were characterized by X-ray crystallography.Display Omitted
Keywords: Copper(II) complex; Cadmium(II) complex; Zinc(II) complex; N,N-di(2-picolyl)cyclohexylmethylamine; Methyl methacrylate polymerization; Syndiotacity;

New members in the [Mn10] supertetrahedron family by Józef Utko; Angelos B. Canaj; Constantinos J. Milios; Maria Sobocińska; Tadeusz Lis (71-74).
Two manganese complexes, [MnII 4MnIII 6Cl4(CH3OCH2CH2O)12 O4][MnII 3TiIVCl6(CH3OCH2CH2O)6] (1) and [MnII 4MnIII 6Cl4(CH3OCH2CH2O)12O4] [Mn4 II Cl10(CH3OCH2CH2OH)4]∙0.5CH3OCH2CH2OH, (2) have been obtained and characterized by single-crystal X-ray diffraction. Both structures consist of the decametallic dicationic [MnII 4MnIII 6Cl4(CH3OCH2CH2O)12O4]2 + core constructed by four vertex-sharing [MnIII 3MnIIO]9 + tetrahedra. Also, these compounds contain the different tetrametallic dianions: [MnII 3TiIVCl6(CH3OCH2CH2O)6]2 − (in complex 1) and [Mn4 IICl10(CH3OCH2CH2OH)4]2 − (in complex 2). Magnetic dc and ac susceptibility measurements for compound (1) show that the dicationic decanuclear magnetic cluster possesses an S  = 12 ± 1 spin ground-state.Two isostructural decanuclear mixed-valent manganese complexes with “supertetrahedral” topology have been obtained and characterized by single-crystal X-ray diffraction. Magnetic studies reveal an S  = 12 ± 1 ground-state for the decametallic core.Display Omitted
Keywords: Manganese; Mixed-valent clusters; Supertetrahedron; Decanuclear complex; Magnetic properties;

Based on the 5-aminodiacetic isophthalic acid (H4adip), two novel luminescent d10 metal coordination polymers have been successfully synthesized under hydrothermal conditions, namely, [Zn2.5(μ 2-OH)(adip)(H2O)2]·3H2O (1), [Cd2(adip)(H2O)4]·2H2O (2). Compound 1 is a two-dimensional network structure based on the metal five-nuclear subunits. It is extraordinary that 2 is a three-dimensional structure containing two different kinds of pores, the dimensions of the pores are 11.46 × 11.13 Ǻ and 11.43 × 7.49 Ǻ, respectively. The photoluminescent properties of 12 were further investigated.Two novel d10 metal coordination polymers have been synthesized under hydrothermal conditions, namely, [Zn2.5(μ 2-OH)(adip)(H2O)2]·3H2O (1), [Cd2(adip)(H2O)4]·2H2O (2). Compound 1 is a two-dimensional network structure based on the metal five-nuclear subunits. 2 is a three-dimensional structure containing two different kinds of pores. The photoluminescent properties of 12 were further investigated.Display Omitted
Keywords: Transition metal; Coordination polymer; Crystal structure; Photoluminescence;

Under light irradiation, (Bu3NH)3[MoV(CN)8]·2H2O reacting with MnClO4·6H2O and NH4SCN leads to the formation of a new three-dimensional cyano-bridged bimetallic complex {(NH4)2[MnII(CH3OH)4][MnII(DMF)]2[MoIV(CN)8]2} (1). X-ray crystallographic analysis reveals that complex 1 crystallizes in a monoclinic space group and contains two different coordination configurations around MnII ions in an asymmetric unit. Specifically, one is six-coordinated while the other is five-coordinated. The magnetic investigation shows that the paramagnetic behavior is only ascribed to MnII ions because MoV has been reduced into diamagnetic MoIV.A three-dimensional octacyanomolybdate complex of {(NH4)2[MnII(CH3OH)4][MnII(DMF)]2[MoIV(CN)8]2} was obtained by light-induced synthesis, which could not be prepared by traditional methods that always keep the reactants in dark. This complex shows a rare five-coordinated environment of Mn in it and its magnetic properties were investigated.Display Omitted
Keywords: Light-induced synthesis; Manganese; Molecular magnetism; Octacyanomolybdate; Three-dimensional;

The octahedral complex Zn(8-quinolinolate)2(H2O)2 in non-aqueous solvents (e.g. chloroform, cyclohexane) undergoes a photolysis: Zn(8-quinolinolate)2(H2O)2  → Zn(OH)2  + 2 8-quinolinole. It is suggested that this photohydrolysis is facilitated by hydrogen bonding. The irradiation (λ > 340 nm) is absorbed by the ligand chromophore. The IL excitation is associated with a charge shift from the coordinated phenolate to the nitrogen of the pyridine ring. As a consequence, the phenolate loses its coordinating ability. The subsequent deactivation is accompanied by the reversal of the charge shift. The regenerated phenolate may now undergo protonation from an adjacent water ligand in competition with the re-coordination to Zn2 +. This system represents a simple model for activation of water which is coordinated to zinc(II). In distinction to the enzymatic function the hydrolysis in our system is initiated by a light switch.Display Omitted
Keywords: Photochemistry; Hydrolysis; Zinc complexes; 8-Qinolinolate complexes;

Two new 3-D Cd(II) coordination polymers (CPs) with 3,5-bi(4-carboxyphenoxy)-benzoic acid (H3 L), namely [Cd3(L)2(H2O)4]·4H2O (1) and [Cd3(L)2(H2O)3]·2H2O (2), were successfully synthesized under hydrothermal condition at 140 °C and 180 °C, respectively. Complex 1 is constructed from 1-D (–Cd–O–) rod-shaped SBUs (secondary building units) and ‘Y’-shaped L ligands. In complex 2, the 3-D network is mediated by 2-D [Cd(COO)2] n layered motifs and ‘T’ and ‘Y’-shaped L ligands. The results show that the reaction temperature plays a key role on the final structures of the complexes. The luminescent properties of the complexes have also been investigated.Two luminescent 3-D CdII MOFs based on a flexible tripodal multicarboxylate ligand and different SBUs have been successfully synthesized by controlling the reaction temperatures.Display Omitted
Keywords: Cadmium(II) MOFs; Reaction temperature; Crystal structures; Luminescence;

Two structurally different praseodymium-organic frameworks with permanent porosity by Osamah Alduhaish; Bin Li; Vladimir Nesterov; Hadi D. Arman; Khalid Alfooty; Abdullah M. Asiri; Hailong Wang; Banglin Chen (89-92).
Two Praseodymium-organic frameworks, [Pr2(NDC)2(NO3)2(DMA)4] (1) and [Pr3(NDC)4.5(DMF)3(H2O)] (2) (H2NDC = 2,6-naphthalenedicarboxylic acid; DMA = N,N-dimethylacetamide; DMF = N,N-dimethylformamide) have been synthesized and structurally characterized. The discrete Pr2(COO)4 cluster and 1D [Pr(COO)3]n rod act as the secondary building units in MOF 1 and MOF 2, respectively, leading to their different structures of 2D sheet and 3D rod-packing. Their permanent porosities have been also established.Two new microporous lanthanide-organic frameworks based on 2,6-naphthalenedicarboxylic acid have been synthesized and structurally characterized exhibiting permanent porosities.Display Omitted
Keywords: Lanthanide-organic framework; Crystal structure; Gas sorption; Metal-organic framework; Porous material;

New hybrid organic–inorganic uranyl selenate, [K(C12H24O6)(H2O)][(UO2)(SeO4)(NO3)] (I), has been prepared by a room-temperature evaporation from the aqueous solutions of uranyl nitrate, selenic acid, potassium nitrate and 18-crown-6 ether. The crystal structure of I [monoclinic, P21/c, a  = 7.2404(2), b  = 21.2024(7), c  = 15.7322(5) Å, β  = 91.5810(10)°, V  = 2414.19(13) Å3, Z  = 4, R 1  = 0.023] is based upon the [(UO2)(SeO4)(NO3)] one-dimensional uranyl nitrate–selenate chains consisting of UO7 pentagonal bipyramids, SeO4 tetrahedra and nitrate groups. The chains are linked to the [K@(18-crown-6)(H2O)]+ complexes via the K+ ―O bonds to form a “multi-axis transporter” {[K@(18-crown-6)(H2O)][(UO2)(SeO4)(NO3)]} bands that are linked together via weak hydrogen bonds only. The infrared spectroscopy data support the structural data.Crystal structure of the new hybrid organic–inorganic uranyl selenate with 18-crown-6 ether molecules has been studied.Display Omitted
Keywords: Uranyl selenates; Potassium; Crown ether; Crystal structure; Topology; Single-crystal X-ray diffraction;

Synthesis and characterization of [S2MoS2Cu(n-SPhF)]2 −(n =  o, m, p) clusters: Potential 19F-NMR structural probes for Orange Protein by Biplab K. Maiti; Teresa Avilés; Isabel Moura; Sofia R. Pauleta; José J.G. Moura (97-100).
Three fluorinated Mo–Cu–thiolate isomers, [Ph4P]2[S2MoS2Cu(n-SPhF)], [n-SPhF  = 2-fluorothiophenol (1a)], 3-fluorothiophenol (1b), and 4-fluorothiophenol (1c)] were synthesized and spectroscopically characterized. The 19F-NMR signal of the fluorine atom in the benzene has different chemical shift for each isomer, which is highly influenced by the local environment that can be manipulated by different solvents and solutes. The fluorine-19 chemical shift is an advantageous NMR structural probe in alternative to 1H-NMR [B.K. Maiti, T. Avilés, M. Matzapetakis, I. Moura, S.R. Pauleta, J.J.G. Moura, Eur. J. Inorg. Chem. (2012) 4159.], that can be used to provide local information on the pocket of the metal cluster in the Orange Protein (ORP).Display Omitted
Keywords: Orange Protein (ORP); Molybdenum–copper–sulfur; 19F-NMR; Structural probe; Local environment;

A new cobalt(II) coordination polymer formulated as [Co2(N3)4(L)] n ·4n H2O (1) (L = tetrakis(3-pyridyloxymethylene) methane) was synthesized by a diffusion method, and structurally and magnetically characterized. In compound 1, the Co(II) chains with double end-to-end (EE) azide bridges are interlinked by the tetrapyridyl ligands into a three-dimensional framework. With both Co(II) and L as 4-connecting nodes, the structure represents the first real example of the 4-connected net topology with point symbol (62·74)(64·7·9)2. Magnetic studies demonstrated that the double EE azide bridges transmit antiferromagnetic interactions along the chain.The first azide-bridged magnetic system derived from a quadritopic organic bridging ligand (L) was obtained. And the double μ-1,3-N3 bridges transmit antiferromagnetic interactions between Co(II) ions along the chain.Display Omitted
Keywords: Cobalt; Azide; Topology; Magnetic properties;

Photochemical synthesis, structure and spectroscopic properties of [W(CO)4(C5H10N)2CH2] by Paulina Kocięcka; Andrzej Kochel; Teresa Szymańska-Buzar (105-107).
Dipiperidylmethane (CH2dipip) coordinates to photochemically created W(CO)4 species to give a tungsten(0) complex [W(CO)4(CH2dipip)]. The structure of the new bidentate amine complex of tungsten(0) was established by spectroscopic methods (NMR, IR, UVVis) in solution and by single-crystal X-ray diffraction studies. A preliminary experiment indicates that the tungsten complex emits light at λmax.  556 nm, when it is excited by λmax.  523 nm in the solid state at room temperature.Dipiperidylmethane (CH2dipip) coordinates to photochemically created W(CO)4 species to give a tungsten(0) complex [W(CO)4(CH2dipip)]. Structure of the new bidentate amine complex of tungsten(0) was established by spectroscopic methods (NMR, IR, UVVis) in solution and by single-crystal X-ray diffraction studies. A preliminary experiment indicates that the tungsten complex emits light.Display Omitted
Keywords: Tungsten; Chelating amine; Photolysis; NMR method; X-ray structure;

Blue emission of a 2D non-interpenetrated zinc coordination polymer constructed through saturated fatty acid ligand by Jin-Shuang Guo; Gang Xu; Shuai-Hua Wang; Ming-Sheng Wang; Ming-Jian Zhang; Guo-Cong Guo; Jin-Shun Huang (108-111).
We report a new non-interpenetrated 2D zinc coordination polymer, [Zn(AA)(BPHY)] n (1) (H2AA = adipic acid, BPHY = 1,2-bis(4-pyridyl)hydrazine), which is a mixed ligand complex. The solid-state sample of 1 exhibits tunable blue emission excited by UV light with the wavelengths from 320 nm to 380 nm. The luminescent mechanism of 1 has been studied by theoretical calculation.A new non-interpenetrated zinc coordination polymer based on saturated fatty acid ligand can display blue emission excited by UV light.Display Omitted
Keywords: Saturated fatty acid; Coordination polymer; Photoluminescence; Theoretical calculation;

A selective colorimetric sensor for Cu2 + in aqueous solution by Yen-Wen Liu; Jiun-Ly Chir; Shan-Teng Wang; An-Tai Wu (112-115).
We synthesized a novel Schiff-based receptor 1, and investigated its binding properties toward various metal ions. Receptor 1 showed a dramatic color change from colorless to red which could easily be detected by the naked-eye upon binding with Cu2 +. The association constant for 1  · Cu2 + in DMSO/H2O (v/v, 1:9) was calculated to be 1.98 × 108  M− 1. With the addition of Na2EDTA to a mixture of receptor 1 and Cu2 +, the solution changed back to its original colorless appearance instantly.Receptor 1 showed a dramatic color change from colorless to red which could easily be detected by the naked-eye upon binding with Cu2 +.Display Omitted
Keywords: Schiff-base; Colorimetric; Chemosensor; Pyridine; Naked-eye;

A facile way to synthesize Er2O3@ZnO core-shell nanorods for photoelectrochemical water splitting by Kai-Hang Ye; Ji-Yu Wang; Nan Li; Zhao-Qing Liu; Shi-Heng Guo; Yun-Ping Guo; Yu-Zhi Su (116-119).
In this study, we demonstrated large-scale Er2O3@ZnO core-shell nanorods with great photoelectrochemical water splitting ability, which were successfully fabricated by a simple and facile electrodeposition. These Er2O3@ZnO core-shell nanorods exhibited improved photocurrent under the light irradiation, which can be attributed to the enhanced donor density by the covered Er2O3.In this paper, we reported a facile method to prepare Er2O3@ZnO core-shell composites and examined their applications as photo-anodes in photoelectrochemical water splitting. The as-fabricated composites exhibited improved photocurrent under the light irradiation, which can be attributed to the enhanced donor density by the covered Er2O3.Display Omitted
Keywords: ZnO; Er2O3; Core-shell; Photoelectrochemical water splitting;

Synthesis, structure and properties of the first organic amine-templated vanadyl pyrophosphate containing two types of helical chains by Hong-Xiang Wan; Wen-Tao Hou; Wei-Wei Ju; Yu Zhang; Hao Miao; You Song; Yan Xu (120-123).
The first organic amine templated vanadyl pyrophosphate, [H2N(CH3)2]2VO(P2O7) (1), has been synthesized at a relatively mild temperature (180 °C) under solvothermal conditions without any pyrophosphates. The structural analysis reveals that compound 1 is constructed by two types of helical chains and protonated dimethylamine cations. Two types of helical chains in 1 are connected through O―V―O linkages to make a double wave-like [VOP2O7]n chain. Magnetic susceptibility measurement of compound 1 indicates antiferromagnetic interactions between V4 + ions, while the observed SHG efficiency is 0.4 times of urea for 1.The compound, [H2N(CH3)2]2VO(P2O7) (1), has been synthesized at a relatively mild temperatures (180 °C) under solvothermal conditions without any pyrophosphates. The structural analysis reveals that two types of helical chains in 1 are connected through O―V―O linkages to make a double wave-like [VOP2O7]n chain. The observed SHG efficiency is 0.4 times of urea for 1.Display Omitted
Keywords: Polyoxovanadate; Pyrophosphate; Structure; Helical chain; Magnetic property;

Efficient photoluminescence from the encumbered platinum(II) porphyrins by Wei Yuan; Yue Zhang; Hui Li; Qingjiang Ren; Yanxiang Cheng (124-126).
Completely enclosed platinum(II) porphyrins exhibit the dramatic improvements in photoluminescence properties since the intermolecular π–π interactions and intramolecular vibrations are effectively suppressed by the encapsulating and steric effect of peripheral bulky and saturated substituents. The absolute photoluminescence quantum yields (PLQY) is up to 0.46–0.55 and significantly improved over their parent PtTPP.The encumbered Pt(II) porphyrins display the dramatic improvements in photoluminescence compared to their parents, and their emission gradually increases with the increase of concentration.Display Omitted
Keywords: Photoluminescence; Porphyrin; Platinum; Intermolecular interaction;

A homochiral Cu(II) coordination polymer built from helical motif based on two V-shaped ligands by Zhi-Liang Zhang; Xiao-Qiang Yao; Ni An; Heng-Chang Ma; Zi-Qiang Lei; Jia-Cheng Liu (127-130).
By using a V-shaped N-containing ligand and a V-shaped carboxylate ligand, we have successfully synthesized a 3D novel copper homochiral coordination polymer, namely [Cu(OPY)(1,3-bdc)]n (complex 1), [1,3-H2bdc = isophthalic acid, OPY = 4,4′-(oxybis(4,1-phenylene))dipyridine]. The compound has been solvothermally synthesized and characterized by IR, elemental analysis, single crystal X-ray diffraction, XRD, UV–vis, and TG analysis. The complex 1 crystallizes in the chiral space group P65 and possesses an unprecedented uninodal 3D 75∙ 8 topology. However, the complex was synthesized by achiral materials. The complex 1 displays a moderate SHG response and its SHG efficiency is about 0.3 times that of urea. In addition, the compound shows high thermal stability.A 3D non-interpenetrated chiral coordination polymer [Cu(OPY)(1,3-bdc)]n has been solvothermally synthesized by using V-shaped N-containing and multi-carboxylate ligands simultaneously without any chiral precursors. The structure of the complex is composed by the exclusively left-handed helical chains and each single chain is generated around the crystallographic 65 axis with a long pitch of 27.99 Å.Display Omitted
Keywords: V-shaped ligand; Cu(II) coordination polymer; Homochiral; Topology; SHG;

The first example of a novel acetylhydroxamate-coordinated oxovanadium(V) complex with hydrazone ligand has been prepared and structurally characterized. The urease inhibitory activity of the complex was assayed, and the molecular docking study was performed. The complex has strong urease inhibitory activity. The introduction of acetylhydroxamate ligand as functional urease inhibitory group may increase the activity of the complex.The first example of a novel acetylhydroxamate coordinated oxovanadium(V) complex with hydrazone ligand was obtained. The complex shows strong urease inhibitory activity with IC50 value of 8.3 ± 1.6 μM.Display Omitted
Keywords: Hydrazone; Acetylhydroxamate; Oxovanadium complex; Crystal structure; Urease inhibition;

Ivy-like extended structure based on Ni mono-substituted Keggin polymolybdophosphate: Self-assembly, structure, catalytic and magnetic properties by Ji-Lei Liang; Hui-Juan Zhang; Yu-Kun Lu; Hai-Ling Guo; Jin-chong Zhao; Meng-Meng Wu; Yun-Qi Liu; Chen-Guang Liu (135-139).
The first example of ivy-like extended structure based on Ni mono-substituted Keggin polyoxomolybdate has been hydrothermally synthesized and characterized. The distorted organic bicapped Keggin POM modified by uncoordinated 4,4΄-bpys serves as an unprecedented synthon for the supramolecular assembly of 3-D frameworks through strong π⋯π stacking interactions. The compound could serve as a potential catalyst in the oxidation of styrene to benzaldehyde.Ivy-like extended structure based on Ni mono-substituted Keggin polymolybdophosphate: self-assembly, structure, and catalytic propertyDisplay Omitted
Keywords: Nickel; Polyoxometalate; Synthon; Self-assembly; Styrene;