Inorganic Chemistry Communications (v.12, #11)

Contents List (iii-viii).

A novel three-dimensional coordination polymer NaCr(C7H3O4N)2(H2O)2 has been synthesized hydrothermally and characterized by single-crystal X-ray diffraction, IR spectra and UV–vis spectra. Two adjacent asymmetry units are linked together through Na–O and a set of intermolecular hydrogen bonds, while generated the finally 3D super molecular network structure.The hydrothermal synthesis of CrCl3·6H2O, NaOH, 2,6-dipicolinic acid (H2dpa), salicylic acid (HSAL) in water and ethanol at 140 °C for 5 days yields a novel 3D coordination polymer NaCr(C7H3O4N)2(H2O)2 (1). In the complex, each Cr center is in a distorted octahedral environment, and coordinates to two nearly perpendicular dpa anions, which act as tridentate ligands. Na(I) is in a compact sixfold coordination with three non-coordination carbonyl oxygen atoms of neighboring asymmetric units, a carboxylate oxygen atom shares coordination with Cr(III) and two aqueous. Two adjacent asymmetric units are linked together through Na–O and a set of intermolecular hydrogen bonds, which generates the finally 3D supermolecular network structure.
Keywords: Hydrothermal synthesis; Chromium(III) complexes; 2,6-Dipicolinic acid; Crystal structure; Spectroscopic properties;

Molecular switching of nickel(ΙΙ) complexes using a hemilabile N,N′-bis(β-carbamoylethyl)1,2-diaminocyclohexane ligand by Min-Shiun Chao; Horng-Hwa Lu; Ming-Liao Tsai; Chien-Min Lin; Tsung-Hsuan Hsieh (1088-1090).
The reaction of NiCl2·6H2O with one equivalent hemilabile diaminodiamide ligand N,N′-bis(β-carbamoylethyl)1,2-diaminocyclohexane (1) gave a pale blue compound [Ni(C12H24N4O2)(H2O)2]2·3H2O·4Cl (2). With two equivalent ligands, 2 was transformed to a yellow species [Ni(C12H22N4O2)]·3H2O (3). The color change could be described as a pH dependent isomerization of the ligand in the solution.The reaction of NiCl2·6H2O with one equivalent hemilabile diaminodiamide ligand N,N′-bis(β-carbamoylethyl)1,2-diaminocyclohexane (1) gave a pale blue compound [Ni(C12H24N4O2)(H2O)2]2·3H2O·4Cl (2). With more than one equivalent ligands, 2 was transformed to a yellow species [Ni(C12H22N4O2)]·3H2O (3) by the Ni–O to Ni–N bond rearrangement at two amide sites of the complex. The color change could be described as a pH dependent isomerization of the ligand. The results presented could be useful in the design of new Ni(II)-based switching materials.
Keywords: Switching; Complex; Diaminodiamide; Ni(ΙΙ);

Supramolecular assembly of a dinuclear Ag(I) complex with discreet Ag2S2 centers by Craig A. Grapperhaus; Jinlan Cui; Robert M. Buchanan; Mark S. Mashuta (1091-1093).
Supramolecular assembly of N,N′-(thiodiethane-2,1-diyl)bis(1-methyl-1H-imidazole-2-carboxamide) and Ag(I) yields a solid with discreet Ag2S2 centers stacked in columns via π-interactions with hydrogen-bonds to triflate in cavities between four neighboring columns.The NS chelate N,N′-(thiodiethane-2,1-diyl)bis(1-methyl-1H-imidazole-2-carboxamide) and its silver(I) complex have been synthesized and characterized by X-ray crystallography. The complex displays a supramolecular structure consisting of discreet Ag2S2 centers stacked in columns along the a-axis via π-interactions. Individual Ag2S2 cores are isolated with no significant interactions between Ag ions.
Keywords: Supramolecular; Silver; Non-covalent interactions; pi-Stacking; Self-assembly;

Organometallic ruthenium complexes with thiosemicarbazone ligands: Synthesis, structure and cytotoxicity of [(η6-p-cymene)Ru(NS)Cl]+ (NS = 9-anthraldehyde thiosemicarbazones) by Floyd A. Beckford; Gabriel Leblanc; Jeffrey Thessing; Michael Shaloski; Brian J. Frost; Liya Li; Navindra P. Seeram (1094-1098).
A series of half-sandwich arene–ruthenium complexes of the type [(η6-p-cymene)Ru(thiosemicarbazone)Cl]+ have been synthesized and their biological activity investigated. The first structurally characterized arene–ruthenium half-sandwich complex with a thiosemicarbazone ligand is reported.A series of half-sandwich arene ruthenium complexes containing bidentate thiosemicarbazone ligands have been synthesized and their biological activity investigated. The compounds have the general formula [(6-p-cymene)Ru(R-ATSC)Cl]X (ATSC = 9-anthraldehyde thiosemicarbazone and R = H, CH3 and C6H5). The crystal structure of [(6-p-cymene) Ru(MeATSC)Cl]Cl have been determined and represents the first structurally characterized arene–ruthenium half-sandwich complex with a thiosemicarbazone ligand. The complexes show good cytotoxic profiles against MCF-7 and MDA-MB-231 (breast adenocarcinoma) as well as HCT 116 and HT-29 (colorectal carcinoma) cell lines.
Keywords: Thiosemicarbazones; Ruthenium–arene complex; DNA interaction; Viscometry; Cytotoxicity; Structure elucidation;

Transition metal ion capture using functional mesoporous carbon made with 1,10-phenanthroline by Wilaiwan Chouyyok; Wassana Yantasee; Yongsoon Shin; Rafal M. Grudzien; Glen E. Fryxell (1099-1103).
Functional mesoporous carbon has been built using 1,10-phenanthroline as the fundamental building block, resulting in a nanoporous, high surface area sorbent capable of selectively binding transition metal ions. This material had a specific surface area of 870 m2/g, an average pore size of about 30 Å, and contained as much as 8.2 wt% N. Under acidic conditions, where the 1,10-phenanthroline ligand is protonated, this material was found to be an effective anion exchange material for transition metal anions like PdCl 4 - 2 and H 2 VO 4 - 1 . 1,10-Phenanthroline functionalized mesoporous carbon (“Phen-FMC”) was found to have a high affinity for Cu(II), even down to a pH of 1. At pHs above 5, Phen-FMC was found to bind a variety of transition metal cations (e.g. Co(II), Ni(II), Zn(II), etc.) from filtered ground water, river water and seawater. Phen-FMC displayed rapid sorption kinetics with Co(II) in filtered river water, reaching equilibrium in less than an hour, and easily lowering the [Co(II)] to sub-ppb levels. Phen-FMC was found to be more effective for transition metal ion capture than ion-exchange resin or activated carbon.Functional mesoporous carbon has been built using 1,10-phenanthroline as the fundamental building block, resulting in a nanoporous, high surface area sorbent capable of selectively binding transition metal ions. This material had a specific surface area of 870 m2/g, an average pore size of about 30 Å, and contained as much as 8.2 wt% N. Under acidic conditions, where the 1,10-phenanthroline ligand is protonated, this material was found to be an effective anion exchange material for transition metal anions like PdCl 4 2 - and H 2 VO 4 1 - . 1,10-Phenanthroline functionalized mesoporous carbon (“Phen-FMC”) was found to have a high affinity for Cu(II), even down to a pH of 1. At pHs above 5, Phen-FMC was found to bind a variety of transition metal cations (e.g. Co(II), Ni(II), Zn(II), etc.) from filtered ground water, river water and seawater. Phen-FMC displayed rapid sorption kinetics with Co(II) in filtered river water, reaching equilibrium in less than an hour, and easily lowering the [Co(II)] to sub-ppb levels. Phen-FMC was found to be more effective for transition metal ion capture than ion-exchange resin or activated carbon.
Keywords: Mesoporous carbon; Nanoporous; Sorbent; Ion exchange; Anion exchange; Metal ion chelation; Natural waters; Water purification; Dialysis; Metal poisoning;

A new open-framework hybrid material [Zn3O3(C13H14N2)3]V6O15 composed of a fully oxidized novel oxometallic framework containing 10-membered {V4ZnO5} rings and 4,4′-trimethylene dipyridine ligands (C13H14N2) has been synthesized and characterized. The compound provides a potentially attractive model to study the structures of metallo-biomolecules by use of solid state NMR techniques.A new hybrid material [Zn3O3(C13H14N2)3]V6O15 (1) with extended framework structure has been synthesized hydrothermally and characterized by vibrational spectroscopy, thermogravimetry and complete single crystal X-ray diffraction analysis. The compound has a complex three-dimensional covalent framework structure. It exhibits a fully oxidized novel oxometallic framework containing 10-membered {V4ZnO5} oxometalate rings and 4,4′-trimethylene dipyridine ligands (C13H14N2) that connect pairs of crystallographically equivalent zinc atoms. The extended structure of 1 may also be viewed as containing a framework of corner-sharing {VO4} and {ZnO2N2} polyhedra together with 4,4’-trimethylene dipyridine ligands linking zinc centers. The hybrid material is thermally stable up to 323 °C. It contains metal centers and coordination geometry that make it a potentially attractive model compound for investigating the structures of metallo-organic biomolecules by use of solid state NMR spectroscopic techniques. Crystal data for C39H42N6O18V6Zn3: monoclinicic P21, a  = 10.9894(9) Å, b  = 18.1493 (15) Å, c  = 13.0903 (11) Å, β  = 109.8880(10)°, V  = 2455.1(4) Å3, Z  = 2, D calc.  = 1.873 Mg/m3.
Keywords: Hybrid material; Oxometalate motifs; Crystal structure; Framework-structure; Solid-state NMR model compound;

This article has been retracted at the request of the Editors because of concerns about the validity of results reported in this article and other publications in Elsevier journals by the same authors, namely:Publication of an article in a peer-reviewed journal is an important building-block in the development of science. Elsevier has defined policies and ethical guidelines and takes its duties of guardianship over the scholarly record extremely seriously.The Editors of the Elsevier journals involved found that the allegations of fraud are conclusive and they have decided that these papers should be retracted from the journals.

C–S bond cleavage in pyridylmethylthioether systems promoted by oxorhenium(V) ion by Biswajit Das; Sandipan Sarkar; Ennio Zangrando; Pabitra Chattopadhyay (1112-1115).
C–S bond cleavage in pyridylmethylthioether systems promoted by oxorhenium(V) ion has been established performing the reaction of 1,2-bis(2-pyridyl-methylthio)ethane(BPT1), 1,3-bis(2-pyridylmethylthio)propane(BPT2) and 3,4-bis(2-pyridylmethylthio)-5-methyltoluene (BPT3) with Bu4N[ReOCl4] in alcoholic medium. Two new oxorhenium(V) complexes of in situ formed new thiol ligands (NSS donor sets) formulated as [ReO(L1)Cl2] (1a) and [ReO(L2)Cl2] (1b) were produced through cleavage of one C–S(thioether) bond in BPT1 and BPT2; where as a binary oxorhenium(V) complex of 3,4-dimercapto-toluene ligand (L3H2) as Bu4N[ReO(L3)2] (1c) through cleavage of two C–S(thioether) bonds in BPT3. The resulting complexes were structurally characterized.C–S bond cleavage in pyridylmethylthioether systems promoted by oxorhenium(V) ion has been established performing the reaction of 1,2-bis(2-pyridylmethylthio)ethane(BPT1), 1,3-bis(2-pyridyl-methylthio)propane(BPT2) and 3,4-bis(2-pyridylmethylthio)-5-methyltoluene (BPT3) with Bu4N[ReOCl4] in dry alcoholoic medium. In case of BPT1 and BPT2, new 2-(2-pyridylmethylthio)ethane-1-thiol (L1H) and 3-(2-pyridylmethylthio)propane-1-thiol (L2H) ligand, respectively were formed in situ through cleavage of one C–S(thioether) bond, resulting in the neutral oxorhenium(V) complexes of formulation [ReO(L1)Cl2] (1a) and [ReO(L2)Cl2] (1b); where as in case of BPT3, binary oxorhenium(V) complex of 3,4-dimercapto-toluene ligand (L3H2), formulated as Bu4N[ReO(L3)2] (1c) through cleavage of two C–S(thioether) bonds. The presence of picolinic acid, as by-product in the filtrates of the C–S bond cleavage reactions in dry alcohol, was detected by treatment of copper(II) salts and GC–MS techniques. But in hydrated alcoholic medium no C–S bond cleavage induced by ReO(V) ion occurred in any of the BPT systems rather the conversion of ReO(V) into perrhenate salt was observed; this reaction mixture, in turn on reaction with copper(II) nitrate trihydrate salt, produce [Cu(BPT)Cl]ReO4 (2) type complexes. The solid-state structures of complexes 1a and 2a were established by X-ray crystallography.
Keywords: C–S bond cleavage; Oxorhenium(V) ion; Crystal structure;

As an expansion to the previous characterization of enzyme inhibitors from silver and metal Schiff base complexes, here describe the Cobalt Schiff base complexes [CoIII(L1)2] (NO3) 1 and Co 3 II ( L2 ) 2 ( C 5 H 5 N ) 6 · 2 ( ClO 4 ) n 2 with ligands derived from 3-formylsalicylic acid as potent inhibitors on Jack Bean Urease (jbU).[CoIII(L1)2] (NO3) 1, Co 3 II ( L2 ) 2 ( C 5 H 5 N ) 6 · 2 ( ClO 4 ) n 2 (where L1 = (3-carboxysalicylidene)-(2-hydroxyaminoethylamine), L2 = (3-carboxysalicylidene)-phenylmethylamine) were synthesized and characterized by elemental analysis, single crystal X-ray diffraction and tested for inhibitive enzymatic activity on Jack Bean Urease(jbU). 1 is a mononuclear complex and the center cobalt atom is chelated by donors of N4O2 possessing a well defined octahedral configuration, and 2 contains two environmentally different cobalt centers, by the μ 2 carboxyl groups bridging the repeat units extending into a one-dimension configuration. Both of the mononuclear neutral molecules 1 and polymeric (1D chain) 2 are future connected via huge inter- and intra-molecular O-H⋯O and C–H⋯O bonds exhibiting a network structure. The enzymatic activity study indicated that the two complexes are showed potent inhibitions against jbU, with IC50 20.31 ± 0.53 μM of 1 and 22.24 ± 0.67 μM of 2, which are about 2 times more than 42.12 ± 0.08 μM of acetohydroxamic acid as positive reference.
Keywords: Cobalt complexes; Crystal structures; Inhibitory activities; Jack Bean Urease;

Bis(1-H-benzo-triazolylmethyl)selenide (L) was synthesized by reacting Se2− generated in situ with 1-(chloromethyl)-1H-benzotriazole. It shows characteristic proton, C-13 and Se-77 NMR spectra. μ-Dichlorobis(η3-allyl)palladium(II) reacts with L resulting in a polymeric complexes which form single crystals of stoichiometry [Pd(η3-C3H5)(L)]·ClO4/PF6·CH3CN (1/2). Their structures are of chain type. The anions ClO 4 - / PF 6 - interlink these chains through hydrogen bonds. The 1 and 2 have been found suitable for catalyzing Heck’s C–C coupling reactions (TON up to 93,000; conversion up to 93%).Bis(1-H-benzotriazolylmethyl)selenide (L) has been synthesized by reacting Se2− generated in situ with 1-(chloromethyl)-1H-benzotriazole. Proton, C-13 and Se-77 NMR spectra of L are characteristic. μ-Dichlorobis(η3-allyl)palladium(II) reacts with L resulting in polymeric complexes which give single crystals of stoichiometry [Pd(η3-C3H5)(L)]·ClO4/PF6·CH3CN (1/2). The single crystal X-ray diffraction analyses of these polymeric species reveal that they have chain type of structures, and anions through non-covalent interactions interlink these chains. On changing anion ClO 4 - with PF 6 - the nature of chain is not affected. The 1/2 have been found suitable for catalyzing Heck’s C–C coupling reactions (TON up to 93,000; conversion up to 93%).
Keywords: 3-Allyl)palladium(II); Bis(1-H-benzotriazolylmethyl) selenide; Polymeric complex; Synthesis; Crystal structure; Heck C–C coupling;

A missing link between discrete POMs and the POMs as building blocks in extended structure by Shu-Yun Shi; Cheng-Ling Pan; Yan Chen; Jia-Ning Xu; Xiao-Bing Cui; Yan Wang; Ji-Qing Xu (1124-1127).
A novel compound PMo 10 VI V 4 IV O 42 Co(Phen) 2 ( H 2 O ) 2 PMo 10 VI V 4 IV O 42 Co(Phen) 2 2 · 2 OH - · 4 , 4 -bpy 1 which represents the missing link between the discrete POMs and the POMs as building blocks in extended structure has already been hydrothermally synthesized and characterized by elemental analysis, IR, UV–Vis, XPS spectrum, TG analysis, study of the magnetic susceptibility and single-crystal X-ray diffraction analysis.A novel compound PMo 10 VI V 4 IV O 42 Co(Phen) 2 ( H 2 O ) 2 PMo 10 VI V 4 IV O 42 Co(Phen) 2 2 · 2 OH - · 4 , 4 -bpy 1 which represents the missing link between the discrete POMs and the POMs as building blocks in extended structure has already been hydrothermally synthesized and characterized by elemental analysis, IR, UV–Vis, XPS spectrum, TG analysis and single-crystal X-ray diffraction analysis. The study of the magnetic susceptibility of the compound 1 demonstrates the presence of ferromagnetic interactions.
Keywords: Polyoxometalate; Hydrothermal synthesis; Missing link; Discrete POMs; POMs in extended structure; Magnetic susceptibility;

New chemosensors based on thiomacrocycle-containing coumarin-343 fluoroionophor: X-ray structures and previous results on the effect of cation binding on the photophysical properties by Hugo M. Santos; Bruno Pedras; Abel Tamayo; Jaume Casabó; Lluis Escriche; Berta Covelo; José Luis Capelo; Carlos Lodeiro (1128-1134).
L1, a new emissive dye derived from coumarin-343 bearing an aza-thio macrocycle ring as chelating unit, and its parent compound L2, without the macrocycle ring, have been synthesized in a very good yield. Both compounds show very promising intensity fluorescence quantum yields. Preliminary results concerning the metal–ion sensing effects are presented. Titrations with Ag+, Pd2+, and Ni2+ have been studied by UV–vis absorption and fluorescence spectroscopy.Two new emissive chemosensors based on coumarin-343 have been synthesized, and their photophysical studies conducted. L1 contains an aza-thio macrocycle ring as the chelating unit, which has great affinity for soft metal ions, whereas L2 is a parent species without macrocyclic unit. Both compounds were separated by column chromatography and characterized by elemental analysis, 1H,13C NMR, UV–vis and FAB mass spectroscopy. The X-ray structures of L1 and L2 and the supramolecular interactions in the solid state are discussed. Preliminary results on the metal–ion sensing effects of the ligands are presented. Titrations with Ag+, Pd2+ and Ni2+ have been studied by UV–vis absorption and fluorescence spectroscopy.
Keywords: Coumarin-343; Molecular chemosensors; Fluorescence; Thio-macrocycles; Transition metals;

Facile synthesis of new Pd(II) and Cu(II) based metallomesogens from ligands containing thiophene rings by Ugo Caruso; Rosita Diana; Barbara Panunzi; Antonio Roviello; Marco Tingoli; Angela Tuzi (1135-1138).
The syntheses of the two thiophene based mesogenic ligands and of their palladium(II) and copper(II) complexes achieved through facile and straightforward procedures is reported. The liquid crystal properties were analyzed also by X-ray diffraction techniques.Very simple synthetic procedures, involving use of tin/amine complex afford two new mesogenic thiophene derivatives. These can chelate palladium(II) or copper(II) producing the corresponding metallomesogens. The liquid crystal properties of all compounds were investigated by calorimetry, polarizing microscopy and X-ray diffraction techniques. Molecular and crystal structure of one ligand and two complexes were analyzed by single crystal X-ray diffraction. Connections between structural features and phase behaviour are discussed.
Keywords: Thiophene; Bent shape; Metallomesogens;

The hydrothermal reaction of ZnCl2, Na6[H2W12O40], and bpy (2,2′-bipyridine) yields a new organic–inorganic hybrid compound, [Zn(bpy)3]1.5[H3W12O40Zn(bpy)2(H2O)]·0.5H2O, in which a metatungstate ion [H3W12O40]5− is linked to a [Zn(bpy)2(H2O)]2+ unit through a bridging oxo group to form a anionic complex [H3W12O40Zn(bpy)2(H2O)]3−. A dimmer is formed between two anionic complexes [H3W12O40Zn(bpy)2(H2O)]3− through hydrogen bonds.A new organic–inorganic hybrid compound, [Zn(bpy)3]1.5[H3W12O40Zn(bpy)2(H2O)]·0.5H2O (bpy = 2,2′-bipyridine) has been synthesized hydrothermally from ZnCl2, Na6[H2W12O40], and 2,2′-bipyridine, and has been analyzed using X-ray crystallography, thermogravimetric analysis and UV–Vis spectroscopy. The compound contains an anionic complex [H3W12O40Zn(bpy)2(H2O)]3− in which α-metatungstate ion [H3W12O40]5− coordinated to a [Zn(bpy)2(H2O)]2+ unit through a bridging oxo group.
Keywords: Polyoxotungstate; Hydrothermal synthesis; Crystal structure; Zinc;

BHandHLYP/6-31G(d,p) calculations and molecular integrations of the quantum theory of atoms in molecules (QTAIM) were applied to study a new class of mC 2 H 5 + ⋯ n ( BeH 2 ) (m  = 1 or 2 and n  = 1 or 2) dihydrogen-bonded hyperconjugation complexes.BHandHLYP/6-31G(d,p) calculations and molecular integrations of the quantum theory of atoms in molecules (QTAIM) were applied to study a new class of dihydrogen-bonded complexes ( mC 2 H 5 + ⋯ nMgH 2 with m  = 1 or 2 and n  = 1 or 2) based on the assumption that earth alkaline hydride MgH2 can bind with the non-localized hydrogen H+ δ of the ethyl cation C 2 H 5 + .
Keywords: Ethyl cation; Hyperconjugation; Dihydrogen bonds; QTAIM;

This article has been retracted at the request of the Editors because of concerns about the validity of results reported in this article and other publications in Elsevier journals by the same authors, namely:Publication of an article in a peer-reviewed journal is an important building-block in the development of science. Elsevier has defined policies and ethical guidelines and takes its duties of guardianship over the scholarly record extremely seriously.The Editors of the Elsevier journals involved found that the allegations of fraud are conclusive and they have decided that these papers should be retracted from the journals.

Synthesis, characterization, thermal study, and crystal structure of a new layered alkaline earth metal sulfonate: Sr[C2H4(SO3)2] by Tolulope O. Salami; Stephanie N. Patterson; Victoria D. Jones; Antonio Masello; Khalil A. Abboud (1150-1153).
A rare two-dimensional layered inorganic–organic hybrid material was obtained by hydrothermal methods. The strontium sulfonate layers are stabilized by –CH2–CH2–groups. The –CH2–CH2– groups are linked to sulfur atoms which in turn bond to the strontium center through bridging oxygen. The structural and thermal properties are discussed.A rare two-dimensional layered inorganic–organic hybrid material, strontium sulfonate Sr[C2H4(SO3)2] was synthesized by hydrothermal reaction of strontium chloride hexahydrate and ethane disulfonic acid at 160 °C. Single-crystal X-ray diffraction was utilized for structural determination. Data showed that the compound, crystallized in the monoclinic system and space group of C2/c. With cell parameters a  = 8.3183(7) Å, b  = 5.4416(5) Å and c  = 14.9784(13) Å. The new material was extensively studied by DRIFT-infrared spectroscopy, thermogravimetric analysis, SEM and powder X-ray diffraction. Results show that the compound is thermally stable.
Keywords: Metal sulfonate; MOF; Layered compound; Organic linkers; Hydrothermal synthesis;

A selective fluorescence probe for yttrium(III) based on acylhydrazone Schiff base by Dong Zhang; Zhipeng Zang; Xiaoyan Zhou; Yan Zhou; Xiaoliang Tang; Ruiping Wei; Weisheng Liu (1154-1156).
A synthesized fluorescence ligand based on acylhydrazone Schiff base can detect the Y3+, a naked-eye color change from colorless to green with a remarkable fluorescence enhancement of L in the presence of Y3+ can be seen in the sun.A new fluorescence probe has been developed for the recognition of Y3+. The probe, 2-hydroxy-1-naphthaldehyde salicyloylhydrazone, L, with Y3+ was studied in detail. Based on the chelation reaction, a highly sensitive colorimetric and fluorescent method was developed for the determination of yttrium in THF; it can detect the trace Y3+ with naked-eye in the sun. The binding mode was investigated by UV–Vis spectra, ESI-TOF MS, IR and XRD.
Keywords: Fluorescence probe; Yttrium(III); Schiff base; Acylhydrazone;

Easy obtainment of three-dimensional coordination polymer of zinc 1,2,4,5-benzenetetracarboxylate with para-amino-pyridinium cations by Archimede Rotondo; Giuseppe Bruno; Fabio Messina; Francesco Nicolò; Fausto Puntoriero (1157-1160).
The described structure evidences a particular anionic 3D metal–organic-framework whose channels are filled by aromatic pyridinium ions. To our knowledge this simple ‘mix and wait’ synthesis, provides a first tip toward the building strategy of associated coordination polymers whose formation can be specifically driven by ancillary hydrogen binding amines.Within a wide study on coordination polymers coming from 1,2,4,5-benzenetetracarboxylate combined with aromatic amines and first row transition metal ions, we isolated and characterized a peculiar tridimensional coordination polymer made by an anionic mesoporous scaffold of Zn(II)-benzeneteracarboxylate whose charge is balanced by included p-aminopyridinium cations stacked up along two quasi-perpendicular crystallographic directions. The particular features of the solid state structure, easily obtained in standard conditions, prompts a wider research of possible related derivatives.
Keywords: X-ray crystallography; Metal–organic-frameworks; Benzene polycarboxylates; Transition metal ions;

Two nickel coordination polymers with flexible ligand 1,3,5-tri(1,2,4-triazol-1-ylmethyl)-2,4,6-trimethylbenzene by Hongliang Wang; Yunfei Feng; Na Liang; Baolong Li; Yong Zhang (1161-1163).
Two coordination polymers [Ni3(ttmb)2(H2O)6Cl6](H2O)3 (1) and [Ni(ttmb)2(H2O)2](NO3)2(H2O)4 (2) (ttmb = 1,3,5-tri(1,2,4-triazol-1-ylmethyl)-2,4,6-trimethylbenzene) were synthesized. Compound 1 forms an undulated (3, 4)-connected two-dimensional network. Each undulated two-dimensional network polycatenates other two identical networks, thus giving a rare (2D → 3D) parallel polycatenation network in 1. Compound 2 constructs a two-dimensional (4, 4) network.The reaction of 1,3,5-tri(1,2,4-triazol-1-ylmethyl)-2,4,6-trimethylbenzene (ttmb) with Ni(II) salts yields two coordination polymers [Ni3(ttmb)2(H2O)6Cl6](H2O)3 (1) and [Ni(ttmb)2(H2O)2](NO3)2(H2O)4 (2). The flexible ligand ttmb shows the cis,cis,cis-conformation and a tri-monodentate coordination mode in 1. Each ttmb links three Ni(II) atoms to form an undulated (3, 4)-connected two-dimensional network. Each undulated two-dimensional network polycatenates other two identical networks, thus giving a rare (2D → 3D) parallel polycatenation network in 1. The ttmb ligand exhibits the cis,trans,trans-conformation and a two-monodentate coordination mode in 2. Each ttmb connects two Ni(II) atoms to construct a two-dimensional (4, 4) network in 2. The thermal stability of compounds 1 and 2 was studied.
Keywords: Polycatenation network; Coordination polymer; Anion role; Nickel complex; 1,3,5-Tri(1,2,4-triazol-1-ylmethyl)-2,4,6-trimethylbenzene;

One new nonlinear optical and ferroelectric one-dimensional chain constructed by an unsymmetric bridging ligand by Yong-Tao Wang; Gui-Mei Tang; Yong-Qin Wei; Ting-Xiao Qin; Tian-Duo Li; Ji-Bei Ling; Xi-Fa Long (1164-1167).
One new one-dimensional neutral chain constructed by an unsymmetric bridging ligand and zinc ion, presents acentric polar packing arrangement, exhibiting second harmonic generation response and ferroelectric behaviors.One new one-dimensional neutral coordination polymer [Zn(BTA)2(H2O)] n (1) was hydrothermally synthesized by the self-assembly of the flexible and unsymmetric bridging ligand, 2-(1H-benzotriazol-1-yl)acetic acid, and zinc nitrate. The induction of the unsymmetric ligand leads it to crystallize in non-centrosymmetric polar packing arrangement, which displays second harmonic generation response and ferroelectric behavior, which provides a new strategy for designing functional coordination compounds.
Keywords: Zinc complex; One-dimensional chain; 2-(1H-benzotriazol-1-yl)acetic acid; Acentric structure; Nonlinear optical; Ferroelectric property;

Hydrothermal synthesis and crystal structure of a luminescent 3D lead(II) coordination polymer [Pb(4-cca)] n (4-cca = 4-carboxycinnamate) by Bing Wu; Zhi-Gang Ren; Hong-Xi Li; Ming Dai; Duan-Xiu Li; Yong Zhang; Jian-Ping Lang (1168-1170).
The reactions of Pb(NO3)2 with 4-carboxycinnamic acid (4-H2cca) in water at pH 6 under hydrothermal conditions afforded a new three-dimensional coordination polymer [Pb(4-cca)] n , which may be viewed as being built of two-dimensional [Pb(COO)2] n layers pillared by –Ph–CH=CH– spacers.A novel lead(II) coordination polymer [Pb(4-cca)] n (1) was prepared by the hydrothermal reaction of Pb(NO3)2 with 4-carboxycinnamic acid (4-H2cca) and structurally characterized. Single-crystal X-ray diffraction revealed that 1 has a 3D supramolecular architecture constructed by 2D [Pb(COO)2] n layers pillared by –Ph–CH=CH– spacers. The thermal and luminescent properties of 1 in the solid state were also investigated.
Keywords: 4-Carboxycinnamic acid; Lead(II); Hydrothermal synthesis; Structure; Luminescent properties;