Inorganic Chemistry Communications (v.10, #6)

Contents List (iii-ix).

Condensation of dipyrromethane, pyrrole-2-carbaldehyde with either 9,9′-spirobifluorene or fluorene aldehyde yields new meso-monosubstituted, β-unsubstituted porphyrins. The large size of spirobifluorene hinders the rotation around the C meso –Caryl bond to give, for bis-ligated complexes, two different topological faces.Condensation of dipyrromethane, pyrrole-2-carbaldehyde with either 9,9′-spirobifluorene or fluorene aldehyde yields new meso-monosubstituted, β-unsubstituted porphyrins. The large size of spirobifluorene hinders the rotation around the C meso –Caryl bond to give, for bis-ligated complexes, two different topological faces.
Keywords: Monoarylporphyrin; Spirobifluorene; Fluorene; Ruthenium; Atropisomer; Nuclear magnetic resonance;

Synthesis, characterization and reactivity of a trinuclear copper(II) thiocyanurate complex: A spin-frustrated molecular propeller by Michael J. Prushan; Natalie K. Privette; Matthias Zeller; Allen D. Hunter; Sam Lofland; Stephen D. Preite (631-635).
[Cu(4-MeIn)]3(TMTA), a trinuclear propeller complex composed of three Cu(4-MeIn) “blades” coordinated to a 2,4,6-trimercaptotriazine (TMTA) “hub”. The complex exhibits moderate antiferromagnetic interactions and is a classic example of a spin-frustrated molecule. After extended periods of time in solution, the complex yields dinuclear products which are a result of desulfurization reaction.1,3-bis{2-(4-methylpyridyl)imino}isoindoline (4-MeInH) reacts with copper(II) acetate and 2,4,6-trimercaptotriazine (H 3 TMTA) to yield [Cu(4-MeIn)]3(TMTA), a trinuclear propeller complex composed of three Cu(4-MeIn) “blades” coordinated to a 2,4,6-trimercaptotriazine (TMTA) “hub”. Each copper(II) center is coordinated via a exocyclic sulfur and a ring nitrogen from TMTA. Although the trimer is infinitely stable in the solid state, dark green solutions fade over time to produce a mixture of dinuclear products which are a result of both hydrolysis and desulfurization reactions. Variable temperature magnetic susceptibility measurements on [Cu(4-MeIn)]3(TMTA) are consistent with a spin-frustrated doublet ground state and show the presence of moderate antiferromagnetic coupling (−2J  = 38.14 cm−1) between the copper(II) centers.
Keywords: Thiocyanuric acid; 2,4,6-Trimercaptotriazine; Copper; Trinuclear; X-ray diffraction; Magnetism;

The first Eu(III) one-dimensional array linked by 2,2′-bipyrimidine, [Eu(hfa)3bpm] n where hfa = 1,1,1,5,5,5-hexafluoroacetylacetonate, has been structurally characterized and the temperature dependent luminescence properties in the solid state and in solution have been studied.The previously reported monometallic Eu(III) complex Eu(hfa)3bpm, where hfa = 1,1,1,5,5,5- hexafluoroacetylacetonate and bpm = 2,2′-bipyrimidine, shows characteristic emissions in the visible region associated with the 5D0  → 7F J (J  = 0–4) transitions of the Eu(III) center. Lifetime measurements are fit to a mono-exponential and are inversely related to temperature. Crystals grown from slow diffusion of hexanes into an ethyl acetate solution of the complex yield an unusual one-dimensional array in which each Eu(III) complex is connected to another through bpm bridging units.
Keywords: Europium; Bipyrimidine; b-diketonate; One-dimensional array; Coordination polymer;

The synthesis of cadmium doped mesoporous TiO2 by Xiaohong S. Li; Glen E. Fryxell; Mark H. Engelhard; Chongmin Wang (639-641).
Cd doped mesoporous titanium oxide was prepared using non-ionic surfactants and easily handled titanium precursors. The Cd doping was found to be stabilize the mesoporous structure.Cd doped mesoporous titanium oxide was prepared using non-ionic surfactants and easily handled titanium precursors. The Cd doping was found to be able to significantly inhibit the growth of anatase crystal size, stabilize the mesoporous structure, and retard the densification of nanoporous TiO2 at elevated temperatures.
Keywords: Mesoporous; Nanoporous; Titanium dioxide; Anatase; Cadmium; Doping; Templated synthesis; Sol–gel; Surfactant; Photocatalyst;

Synthesis and characterization of phosphate-coated mesoporous titania and Cd-doping of same via ion-exchange by Yongsoon Shin; Bruce W. Arey; Chongmin Wang; Xiaohong S. Li; Mark H. Engelhard; Glen E. Fryxell (642-645).
Phosphate-based mesoporous TiO2 was prepared, producing a structure of 400 nm hollow beads, containing interfacial phosphate groups, which are effective ion-exchange sites for transition metal cations.Phosphate-based mesoporous TiO2 materials were prepared by surfactant-directed method using an alkylphosphate surfactant, which produced a mesoporous titania with high surface area (∼200 m2/g) and a phosphate monolayer interface. Calcination of the as-synthesized greenbody in an ozone atmosphere generated materials with higher surface area, and higher purity, than did calcination in air. These interfacial phosphate groups are convenient functionality for chemically modifying the surface via ion-exchange processes. High doping ratios of P/Ti (0.47–0.69) and Cd/P (0.37–0.40) were observed. Materials were characterized by XRD, FE-SEM, TEM, and XPS.
Keywords: Phosphate-based TiO2; Cd-doping; Ozone; Mesoporous; Ion exchange; Templated synthesis;

Anion binding in self-assembled monolayers in mesoporous supports (SAMMS) by Shas V. Mattigod; Glen E. Fryxell; Kent E. Parker (646-648).
The binding of various anions to cationic transition metal complexes lining the pores of mesoporous silica is characterized and correlated to anion basicity.The binding of various anions to cationic transition metal complexes lining the pores of mesoporous silica is characterized and correlated to anion basicity.
Keywords: Mesoporous; Nanoporous; Metal complex; Anion; Anion binding; Mechanism;

A novel 3D metal-organic framework, Cd(N2C6O2H12)3  · 2(NO3) (1), has been synthesized under mild conditions, the single-crystal X-ray diffraction revealed that the ligand dabco(1,4-diaza-bicyclo[2.2.2]octane) was oxidized to its N-oxide in situ and polymer 1 had a non-interpenetrated pcu topology.A novel 3D metal-organic framework, Cd(N2C6O2H12)3  · 2(NO3) (1), has been synthesized under mild conditions; the single-crystal X-ray diffraction revealed that the ligand dabco(1,4-diaza-bicyclo[2.2.2]octane) was oxidized to its N-oxide in situ and polymer 1 had a non-interpenetrated pcu topology, which is also known as α-polonium-type.
Keywords: Metal-organic framework; Crystal structure; Pcu topology; Oxide;

Synthesis and X-ray single crystal structure analysis of an inorganic nucleoside analog by Srećko I. Kirin; Kristi Ohr; Hemant P. Yennawar; Christopher M. Morgan; Lauren A. Levine; Mary Elizabeth Williams (652-656).
The Cu(II) containing nucleoside analog 3 was synthesized and fully characterized, including X-ray analysis. In the solid state 3 assembles by apical Cu–O bonds into a coordination polymer, with short Cu–Cu distances of 5.32 and 5.78 Å. The X-ray structure of 3 is in accordance with an isotactic structural model for charge neutral inorganic nucleic acids analogs.The inorganic nucleoside analog [Boc-aeg{Cu(pda)py-Ac}-OMe] (3) is prepared and fully characterized. The X-ray single crystal analysis reveals that 3 assembles by apical Cu–O bonds into a coordination polymer, with short Cu–Cu distances of 5.32 and 5.78 Å. The solid state structure of 3 is in accordance with an isotactic structural model for charge neutral inorganic nucleic acids analogs. Aeg = (2-aminoethyl)glycine, py-Ac = 4-acetyl pyridine, pda = pyridine-2,6-dicarboxylic acid.
Keywords: Artificial peptide; Bioinorganic chemistry; Coordination polymer; Cu(II) complex; Nucleic acid analog; X-ray;

1,1-Azido bridge driven aggregation of a centrosymmetric trinuclear linear CoIIICoIICoIII complex by Debashree Mandal; Masahiro Mikuriya; Hoong-Kun Fun; Debashis Ray (657-660).
A trinuclear mixed valence linear Co 2 III Co II complex with only EO azido bridge has been assembled and identified in the solid state from a reaction of metal salt and ligand in presence of N 3 - ions. In absence of N 3 - ions the mononuclear tris chelate is formed exclusively.Reactions of Co(OAc)2  · 4H2O with NaQ (sodium salt of 8-quinolinol) in methanol in absence and presence of NaN3 give the mononuclear complex mer-CoQ3  · MeOH (1) and a linear trinuclear mixed valence complex [Co3(N3)4Q4(OH2)2] · 2H2O (2). Presence of N 3 - ions prevents the formation of tris chelate leading to an aggregation to 2. Four N 3 - anions bridges three cobalt ions all in μ-1,1 coordination mode, resulting in a trinuclear structure with a center of inversion. The complex contains a high-spin CoII and two terminal low-spin CoIII.
Keywords: Bidentate; Linear; Trinuclear; Crystal structure; Magnetic properties;

Two copper(II) complexes, Cu2{3,5-(NO2)2sal}2(2,2′-bipy)2  · 0.5H2O (1) and [Cu2{3,5-(NO2)2sal}2(4,4′-bipy)(H2O)2] n (2) (3,5-(NO2)2sal = 3,5-dinitrosalicylate), were synthesized by hydrothermal reactions and characterized by single crystal X-ray analysis. Complex 1 is in cyclic dimer structure. Complex 2 exhibits a novel 2D herringbone-like network structure built from helical motif. Variable temperature magnetic measurement reveals small ferromagnetic interactions in complex 1.Two copper(II) complexes, Cu2{3,5-(NO2)2sal}2(2,2′-bipy)2  · 0.5H2O (1) and [Cu2{3,5-(NO2)2sal}2(4,4′-bipy)(H2O)2] n (2) (3,5-(NO2)2sal = 3,5-dinitrosalicylate, 2,2′-bipy = 2,2′-bipyridine, 4,4′-bipy = 4,4′-bipyridine), were synthesized by hydrothermal reactions and characterized by single crystal X-ray analysis. There are discrete cyclic binuclear structure in 1 and 2D herringbone-like network structure in 2, although bridging ligand 3,5-(NO2)2sal in 1 and 2 has same coordination model. Variable temperature magnetic measurement reveals small ferromagnetic interactions in complex 1.
Keywords: Hydrothermal synthesis; 3,5-dinitrosalicylate; Herringbone; Dimer; Magnetic property;

In this work, we have synthesised and characterized 17 gold–phosphine mixed ligand complexes using catecholate ion (CA2−). The CA2− is a well-known chelating as well as bridging ligand. In this case it forms Gold(I) two coordinate linear complexes and Gold(III) square planar four coordinate complexes with quinonoid end. The complexes are fully characterised by IR, 1H NMR, 19F(1H) NMR, 31P(1H) NMR, 13C(1H) NMR, 1H–1H COSY NMR and ES/MS mass spectrometry. 31P(1H) NMR technique helps to get the correct assignment regarding the new complex nature.Ag+-assisted dechlorination of Gold(I) and Gold(III) phosphine complexes followed by the reaction with catecholes (H2CA) in the presence of Et3N gives neutral violet complexes, whereas 19, 8a, 1416 are Gold(I) two coordinate linear complexes and 1013 are Gold(III) square planar four coordinate complexes. The 17 new complexes are characterised by ESIMS, IR and multinuclear NMR (1H, 13C, 19F, 31P) spectroscopic studies. In addition, dimensional NMR studies like 1H–1H COSY permit a complete assignment of the complexes in the solution phase.
Keywords: Gold(I); Gold(III); Catechol; Phosphine; 1H; 3C; 19F; 31P; COSY; NMR; ESIMS;

A binuclear Pd(II) complex [Pd2(μ-dppz)2(Hida)2] ·  CH3OH · 2H2O (1) and a mononuclear Pt(II) complex [Pt(Hdppz)(2,6-dipic)] · CH3OH (2), where dppz = 3,5-diphenylpyrazolate, ida = iminodiacetate and 2,6-dipic = 2,6-pyridinedicarboxylate have been synthesized and structurally characterized. Complex 1 forms a 2D network, whereas complex 2 forms a 1D helical network. The luminescence property and antimicrobial activity of the complexes are also investigated.A pyrazolate bridged binuclear Pd(II) complex [Pd2(μ-dppz)2(Hida)2] · CH3OH · 2H2O (1) (dppz = 3,5-diphenylpyrazolate) with monoprotonated iminodiacetate (Hida) and a mononuclear Pt(II) complex containing Hdppz and 2,6-pyridinedicarboxylate (2,6-dipic) [Pt(Hdppz)(2,6-dipic)] · CH3OH (2) have been synthesized and characterized by elemental analysis, 1H NMR, ESI-MS and single crystal X-ray diffraction studies. The molecular packing for 1 shows a 2D network while that for 2 constitutes a left-handed 1D helix. Moderate luminescence property and antimicrobial activity against Bacillus subtilis have been noted for both.
Keywords: Binuclear Pd(II) complex; Mononuclear Pt(II) complex; 2D and helical network; Luminescence; Antimicrobial activity;

A new dioxomolybdenum(VI) complex with an amino acid functionalized Schiff base ligand has been synthesized and characterized by single crystal X-ray structure determination, which reveals an extensive hydrogen bonding in the crystal lattice. This complex is an efficient catalyst for the peroxidic oxidation of sulfides.A cis-dioxomolybdenum(VI) complex with an amino acid functionalized hydrazone ligand derived from salicylaldehyde and Boc-protected β-alanine hydrazide (Boc =  t-butyloxycarbonyl) has been synthesized. The X-ray crystal structure reveals a distorted octahedral geometry at the molybdenum atom with an O5N donor set and vast hydrogen bonding interactions including the amino acid side chain of the ligand. The new cis-dioxomolybdenum(VI) complex is an efficient catalyst for the peroxidic oxidation of sulfides, but does not show any activity towards the oxidation of bromide.
Keywords: Dioxomolybdenum complex; N-salicylidene hydrazides; Amino acids; Crystal structure; Hydrogen bonding interaction; Oxidation catalysis; Sulfoxidation;

A selective colorimetric chemosensor for detecting SO 3 2 - in neutral aqueous solution by Jian Xu; Kai Liu; Duolong Di; Shijun Shao; Yong Guo (681-684).
The colorimetric sensor based on the charge-transfer complex showed high sensitivity for SO 3 2 - in a neutral buffered water/organic solvent system. The experiments confirmed that the color change of the dipyrromethane-TCNQ complex solution in the presence of SO 3 2 - is ascribed to the competitive binding of SO 3 2 - to TCNQ subunit and is proved to be a reversible procedure.As a colorimetric anion sensor, the non-covalent charge-transfer complex, formed by di(hydroxymethyl)-di-(2-pyrrolyl) methane 1 and TCNQ 2, may be used for higher sensitive and selective detection of SO 3 2 - than other inorganic anions in a neutral buffered aqueous system. The excellent system properties is hopeful to be used in the monitoring fields of food products and environmental pollutant.
Keywords: Anion; Charge-transfer complex; Sulfite detection; Chemosensor;

Three coordination polymers of Zn, and Cd were prepared by using flexible bis(imidazolyl) ligands and carboxylate ligands, and their structures were characterized through X-ray diffraction. The compounds exhibit 1D chain, 2D grid network structures. The emissive properties were also studied.Coordination polymers [Zn(imc)(L1)] · H2O, (1, imc = iminodiacetate, L1  = bis(N-imidazolyl)methane) [Zn(hba)2(L2)]2  · EtOH · 3H2O, (2, hba =  p-hydroxybenzoate, L2  = bis(N-benzimidazolyl)methane), [Cd(mal)(H2O)(L3)](3, L3  = 1,4-bis(N-imidazolyl)butane, mal = maleate) have been prepared and structurally characterized. Complex 1 consists of hexa-coordinated central Zn ions and exhibits 2D network structure. The Zn atoms in 2 have tetrahedral coordination geometry, and are linked by bis(imidazolyl) ligands into 1D chain structure. The cadmium ions in 3 are hepta-coordinated with pentagonal bipyramidal geometry. Complex 3 displays 2D grid structure. The TGA showed that the coordination polymers are stable up to 200 °C. All the three complexes are emissive at room temperature in their solid state.
Keywords: Zn(II); Cd(II); Emission; Coordination polymers;

Structural diversity in the borohydrido lanthanides series: First isolation and X-ray crystal structure of ionic [ Sm ( BH 4 ) 2 ( THF ) 5 ] + [ Cp ∗ ′ Sm ( BH 4 ) 3 ] - by Fanny Bonnet; Marc Visseaux; Abderrafia Hafid; Denise Baudry-Barbier; Marek M. Kubicki; Estelle Vigier (690-694).
Two new borohydrido complexes of samarium were prepared: [ Sm ( BH 4 ) 2 ( THF ) 5 ] + [ Cp ∗ ′ Sm ( BH 4 ) 3 ] - (1) and Cp 2 ∗ ′ Sm(BH 4 ) ( THF ) (3) ( Cp ∗ ′ = C 5 Me 4 n Pr ). X-ray studies revealed that 1 displays an unprecedented ionic structure comprising a half samarocene moiety, whereas 3 is monomeric and bears a terminal BH4 ligand.The reaction of Sm ( BH 4 ) 3 ( THF ) 3 with a half equivalent of KCp ∗ ′ ( Cp ∗ ′ = C 5 Me 4 n Pr ) affords a compound comprising one Cp ∗ ′ ligand and three THF molecules per two Sm atoms, [ Cp ∗ ′ Sm 2 ( BH 4 ) 5 ( THF ) 3 ] , according to analytical data. Crystals of penta-THF adduct 1, showing the same 1H NMR spectrum except for the quantity of THF, could be isolated from a solution of half-samarocene Cp ∗ ′ Sm ( BH 4 ) 2 ( THF ) (2). X-ray structure determination of 1 revealed an ionic compound [ Sm ( BH 4 ) 2 ( THF ) 5 ] + [ Cp ∗ ′ Sm ( BH 4 ) 3 ] - with two discrete mononuclear Sm polyhedrons. The expected neutral samarocene Cp 2 ∗ ′ Sm ( BH 4 ) ( THF ) (3) could be obtained from the reaction of Sm ( BH 4 ) 3 ( THF ) 3 with two equivalents of KCp ∗ ′ . X-ray structure analysis showed that 3 is a monomeric complex bearing a terminal borohydride ligand. All BH 4 - ligands in 1 and 3 exhibit an η 3 - H 3 BH bonding mode.
Keywords: Samarium; Borohydride; Early lanthanides; Monocyclopentadienyl;

By using three ligand isomers H2L1, H2L2, and H2L3 [H2L1 = 4,6-bis(2-pyridyl)-2-aminopyrimidine, H2L2 = 4-(2-pyridyl)-6-(3-pyridyl)-2-aminopyrimidine, H2L3 = 4-(2-pyridyl)-6-(4-pyridyl)-2-aminopyrimidine], three copper (I/II) complexes with different structural motifs were synthesized and characterized by single-crystal X-ray diffraction.Three copper(I/II) complexes [Cu2(HL1)2Cl] n (1), [Cu(H2L2)Cl] n (2), and [Cu2(H2L3)Cl2] n (3) were synthesized by the reaction of CuCl2  · 2H2O with three isomers of 4,6-dipyridyl-2-aminopyrimidine: H2L1, H2L2, and H2L3 under hydrothermal conditions. Although in compounds 13, the three ligands all exhibit bridging coordination modes, the structures of the resultant 1D polymers are very different. This result indicates that the structural motif of compounds 13 could be directed by the ligand isomers.
Keywords: Cu(I) complexes; Mixed-valent Cu(I/II) complexes; N,N′-Chelating ligand; 2-Aminopyrimidine-type ligands; Crystal engineering;

Synthesis and structural characterization of tris(phenolate)amine complexes of antimony derived from [ κ 4 -N ( CH 2 Ar Bu 2 t O ) 3 ] Sb by Bryte V. Kelly; Edward C. Weintrob; Daniela Buccella; Joseph M. Tanski; Gerard Parkin (699-704).
The antimony aryloxide compound [ κ 4 -N ( CH 2 Ar Bu 2 t O ) 3 ] Sb reacts with Br2 to give N ( CH 2 Ar Bu 2 t O ) 3 ] SbBr 2 , while Me3NO · 2H2O yields the oxo and hydroxo complexes { [ κ 4 - ( N ( CH 2 Ar Bu 2 t O ) 3 ] Sb ( μ -O ) } 2 , [ κ 4 -N ( CH 2 Ar Bu 2 t O ) 3 ] Sb ( OH ) 2 , and { [ κ 4 -N ( CH 2 Ar Bu 2 t O ) 3 ] Sb VO } 4 { Sb 4 III O 6 } .The antimony aryloxide compound [ κ 4 -N ( CH 2 Ar Bu 2 t O ) 3 ] Sb may be readily obtained via the reaction of Sb(OEt)3 with tris(3,5-di-t-butyl-2-hydroxybenzyl)amine, N ( CH 2 Ar Bu 2 t OH ) 3 . [ κ 4 -N ( CH 2 Ar Bu 2 t O ) 3 ] Sb forms the adduct [ κ 4 -N ( CH 2 Ar Bu 2 t O ) 3 ] Sb ( OSMe 2 ) upon treatment with Me2SO, and comparison of the molecular structure of [ κ 4 -N ( CH 2 Ar Bu 2 t O ) 3 ] Sb ( OSMe 2 ) with that of [κ4-N(o-C6H4O)3]Sb(OSMe2) demonstrates that the Sb–OSMe2 bond length in the former complex is significantly longer than that in the latter. This observation indicates that the [ κ 4 -N ( CH 2 Ar Bu 2 t O ) 3 ] ligand engenders a less Lewis acidic antimony center than does [ κ 4 -N ( o – C 6 H 4 O) 3 ] . [ κ 4 -N ( CH 2 Ar Bu 2 t O ) 3 ] Sb exhibits diverse reactivity. For example, treatment of [ κ 4 -N ( CH 2 Ar Bu 2 t O ) 3 ] Sb with AcOH cleaves one of the Sb–O bonds to give [ κ 3 -N ( CH 2 Ar Bu 2 t O ) 2 ( CH 2 Ar Bu 2 t OH ) ] Sb ( κ 1 - O 2 CMe ) , Br2 undergoes oxidative addition to give N ( CH 2 Ar Bu 2 t O ) 3 ] SbBr 2 , while Me3NO · 2H2O yields the oxo and hydroxo complexes { [ κ 4 -N ( CH 2 Ar Bu 2 t O ) 3 ] Sb ( μ -O ) } 2 , [ κ 4 -N ( CH 2 Ar Bu 2 t O ) 3 ] Sb ( OH ) 2 , and { [ κ 4 -N ( CH 2 Ar Bu 2 t O ) 3 ] Sb V O } 4 { Sb 4 III O 6 } .
Keywords: Antimony; Aryloxide; Bromide; Oxo; Hydroxide;

Puckered-boat conformation (H2O)14 cluster on the self-assembly of an inorganic-metal-architecture by Ping Li; Yongcai Qiu; Jianqiang Liu; Yun Ling; Yuepeng Cai; Shantang Yue (705-708).
BDC (phthalic acid) reacts with EuCl3 to form 1D coordination polymer, in the presence of phen (1,10-phenanthroline) under hydrothermal conditions. Puckered-boat-shaped (H2O)14 water clusters resulted from four free water molecules and six coordinated water molecules.BDC (phthalic acid) reacts with EuCl3 to form 1D coordination polymer, in the presence of phen (1,10-phenanthroline) under hydrothermal conditions. Puckered-boat-shaped (H2O)14 water clusters resulted from four free water molecules and six coordinated water molecules, which join these chains to make a sheet. Of further interesting, the water clusters associate into an inorganic (carbon-free) sheet with chlorine anions by hydrogen bonds. This hybrid water–chlorine configuration acts as a “host” supporting the metal-organic “guest”.
Keywords: Eu complexes; Hydrothermal synthesis; Water cluster; Phthalic acid;

A new dinuclear copper(II) compound, [Cu2(L1-O)2] (1) and zigzag chain polymer, {[FeCl2(L2)]} n , (2) were synthesized by solvothermal reactions and structurally characterized. The methyl group hydroxylation reaction and the redox reaction have been observed in the preparation of 1 and 2, respectively.A new dinuclear copper(II) compound, [Cu2(L1-O)2] (1) (L1 = (4E)-4-(2-hydroxybenzylideneamino)-1,2-dihydro-2,3-dimethyl-1-phenylpyrazol-5-one), and zigzag chain polymer, {[FeCl2(L2)]} n (2) (L2 = 1,5-dimethyl-2-phenyl-4-{[(1E)-pyridine-4-ylmethylene]amino}-1,2-dihydro-3H-pyrazol-3-one), were synthesized by solvothermal reactions and structurally characterized. The methyl group hydroxylation and the redox have been observed in the preparation of 1 and 2, respectively.
Keywords: Dinuclear copper(II); Iron(II) polymer; Solvothermal synthese; Methyl group hydroxylation; Redox;

Nature of intramolecular interactions in hypercoordinate C-substituted 1,2-dicarba-closo-dodecaboranes with short P⋯P distances by Markku R. Sundberg; Rolf Uggla; Clara Viñas; Francesc Teixidor; Sari Paavola; Raikko Kivekäs (713-716).
Experimental and computational evidence show that there is short intramolecular distance between two phosphorus atoms in 1,2-(diphenylphosphino)-1,2-dicarba-closo-dodecaborane. At the B3LYP/6-31G level, quantum theory – atoms-in-molecules indicates direct P⋯P interaction, while natural bonding orbitals describes it mainly as donor–acceptor interaction between phosphorus electron lone pair and adjacent antibonding P–C(phenyl) orbital.Experimental (single-crystal X-ray diffraction) and computational evidence shows that there is short intramolecular distance between two phosphorus atoms in 1,2-(diphenylphosphino)-1,2-dicarba-closo-dodecaborane. In the optimized structure at the B3LYP/6-31G level of theory the interaction was analyzed by quantum theory – atoms-in-molecules and natural bonding orbitals methods. Both methods established the interaction. The former method indicates direct P⋯P interaction, while the latter describes it as donor–acceptor interaction between phosphorus electron lone pair and adjacent antibonding P–C(phenyl) orbital.
Keywords: Carborane; Phosphorus; Intramolecular interaction; QTAIM; NBO;

Luminescent staircase copper(I) coordination polymer based on planar Cu3I3 by Tae Ho Kim; Yong Woon Shin; Jae Sang Kim; Shim Sung Lee; Jineun Kim (717-719).
[Cu3I3 L] n (1) has been synthesized by the reaction of CuI and 1,4-bis((cyclohexylthio)acetyl)piperazine (L). Structural and photophysical studies of 1 in solid state are reported. The bonding of Cu3I3 produces staircase polymers interconnected by the sulfur atoms of L.Copper(I) coordination polymer [Cu3I3 L] n (1) has been synthesized by the reaction of CuI and 1,4-bis((cyclohexylthio)acetyl)piperazine (L). Structural and photophysical studies of 1 in solid state are reported. The bonding of Cu3I3 produces staircase polymers interconnected by the sulfur atoms of L.
Keywords: Copper(I) iodide; Coordination polymer; Dithioether ligand; Crystal structure; Supramolecular assembly;

A chiral 3D polymer with right- and left-helices based on 2,2′-biimidazole: Synthesis, crystal structure and fluorescent property by Yao-Mei Fu; Ya-Hui Zhao; Ya-Qian Lan; Yong Wang; Yong-Qing Qiu; Kui-Zhan Shao; Zhong-Min Su (720-723).
Reaction of cadmium(II) and 2,2′-biimidazole (H2biim) which is partially deprotonated by sodium hydroxide gives a 3D chiral framework with diamond topology. Moreover, the compound exhibits good luminescence at room temperature.A novel three-dimensional (3D) polymer [Cd2(Hbiim)4] n (H2biim = 2,2′-biimidazole) 1 was obtained through hydrothermal reaction and characterized by single crystal X-ray diffraction, and the fluorescent property was also determined. Compound 1 crystallizes in a monoclinic chiral space group P21 and contains two types of helical chains. Hbiim partially deprotonated of H2biim exhibits two different coordination modes, which contributes greatly to the formation of the 3D chiral framework. Compound 1 exhibits blue fluorescence at 488 nm in the solid-state upon excitation at 430 nm.
Keywords: Hydrothermal reaction; 2,2′-Biimidazole; Chirality; Helical structure; Fluorescent property;

Reaction of SnCl2 with the bisthiosemicarbazone ligand ATSMH2 led to the formation of the octahedral tin(IV) complex [Sn(ATSM)Cl2] (1) comprising one doubly deprotonated ligand occupying the equatorial positions and two axial chlorides. Reaction with SnI4 gave [Sn(ATSM)2] (2), containing two doubly deprotonated ligand giving a distorted dodecahedral geometry.Reaction of SnCl2 with the bisthiosemicarbazone ligand ATSMH2 led to the formation of the octahedral tin(IV) complex [Sn(ATSM)Cl2] (1) comprising one doubly deprotonated ligand occupying the equatorial positions and two axial chlorides. Reaction with SnI4 gave [Sn(ATSM)2] (2), containing two doubly deprotonated ligands giving a distorted dodecahedral geometry. The complexes were characterised by elemental analysis, mass spectrometry, 13C and 119Sn CP/MAS NMR and in the case of complex 2 by X-ray diffraction.
Keywords: Thiosemicarbazones; Tin; Structure elucidation; Eight-coordinate complex;

Synthesis of a novel doubly strapped zinc porphyrin and its recognition property for anions by Xiaoping Bao; Hao Zhang; Zhi Zhang; Lei Wu; Zaoying Li (728-730).
A novel doubly strapped zinc porphyrin (2) was synthesized, characterized and studied as anion receptor. It showed a very high affinity and selectivity for H 2 PO 4 - , F and AcO over other anions by combining Lewis acidic binding site (Zn2+) with NHs of the urea groups.A novel doubly strapped zinc porphyrin (2) was synthesized, characterized and studied as anion receptor. It showed a very high affinity and selectivity for H 2 PO 4 - , F and AcO over other anions by combining Lewis acidic binding site (Zn2+) with NHs of the urea groups. In contrast, free base porphyrin (1) and ZnTPP did not show detectable affinities for all the anions examined.
Keywords: Doubly strapped zinc porphyrin; Hydrogen bonds; Lewis acidic binding; Anion receptor;

Structure and optical properties of a 2,3,4,5-functionalized spirobisilole 2,3,3′,4,4′5-hexaphenyl-1,1′-siprobisilole.Spiro-linked orthogonal bisilole, 2,3,3′4,4′5-hexaphenyl-1,1′-spirobisilole, has been synthesized and characterized. Its crystal structure and optical properties were also investigated. This compound shows high thermal stability and strong bluish-green emission(λ max  = 509 nm) with high PL efficiency (55 ± 5%).
Keywords: Spirobisilole; X-ray structure; Optical properties;