Inorganic Chemistry Communications (v.12, #12)

Author index (I-VI).

Contents List (iii-ix).

Improved synthesis of pincer ligand precursor, and synthesis and structural characterization of terphenyl scaffolded S–C–S palladium pincer complex by Paul M. Schroder; Thomas F. Spilker; Wilson Luu; James B. Updegraff; Man Lung Kwan; Paul R. Challen; John D. Protasiewicz (1171-1174).
A quicker preparation of terphenyl pincer ligand intermediate has been developed, and used to prepare a new S–C–S pincer ligand precursor. The new S–C–S palladium pincer complex has been prepared from this ligand precursor and structurally characterized.An easier and more expedient synthesis of 2,6-(BrCH2C6H4)2-4-I-C6H3 (2) is reported. This material allowed easy synthesis of the new pincer ligand precursor 2,6-(4-CH3C6H4SCH2C6H4)2-4-I-C6H3 (3) in 87% yield. Compound 3 reacts with Pd2(dba)3 to give the new palladium pincer complex 4. Compound 4 has been fully characterized, including structural characterization by single crystal X-ray diffraction methods. The results of the crystallographic work on 4 reveal a twisted type pincer complex not unlike related terphenyl pincer complexes.
Keywords: Pincer complex; Sulfur; Palladium; Bromination; Structure;

One-pot approach in the presence of 1H-imidazole-4-carbaldehyde, (S,S)-1,2-diaminocyclohexane and Cu(ClO4)2·6H2O or Ni(ClO4)2·6H2O in methanol gives rise to the bisubstituted and monosubstituted chiral Schiff base-containing compounds 1-Cu and 2-Ni, respectively. Both complexes show normal dielectric behaviors at room temperature with ignorable dielectric losses.Two chiral Schiff base-containing complexes, [Cu(L1)](ClO4)2·H2O (1, L1  = (S,S)-N1,N2-bis((1H-imidazol-4-yl)methylene)cyclohexane-1,2-diamine) and [Ni(L2)2](ClO4)2 (2, L2  = (S,S)-N1-((1H-imidazol-4-yl)methylene)cyclohexane-1,2-diamine) were synthesized from the reaction mixture of 1H-imidazole-4-carbaldehyde, (S,S)-1,2-diaminocyclohexane and Cu(ClO4)2·6H2O or Ni(ClO4)2·6H2O in methanol. Single-crystal X-ray diffraction analyses reveal that the in situ generated chiral Schiff base ligands L1 and L2 are bisubstituted and monosubstituted, respectively, corresponding to the different metal ions CuII and NiII. Variable-frequency and -temperature dielectric properties of 1 and 2 have been studied.
Keywords: In situ; Chiral Schiff base; Copper; Nickel; Dielectric;

A new 1D chain octacyanotungstate-manganese complex shows ferrimagnetic behaviour with two different antiferromagnetic coupling constants obtained by fitting between Mn and W ions.An octacyanotungstate(V)-manganese(II) bimetallic assembly [Mn(Me2-bipy)2]3[W(CN)8]2·9H2O (1) (Me2-bipy = 4,4′-dimethyl-2,2′-bipyridine) was synthesized in methanol and characterized by X-ray crystallography. X-ray analysis shows that complex 1 is a neutral, one-dimensional (1D) infinite chain polymer. Magnetic data analysis demonstrates a long-range magnetic interaction and two different antiferromagnetic coupling constants obtained by fitting between Mn and W ions in 1.
Keywords: Octacyanotungstate; Cyano-bridged; Manganese complex; Crystal structure; Magnetic properties;

A unique polyoxotungstate constructed by parallel stacking helices by Peng-Tao Ma; Dong-Qin Bi; Jing-Ping Wang; Wei Wang; Jing-Yang Niu (1182-1184).
The first polyoxotungstate with helical WO6-octahedral chains of different handedness as building blocks is reported, and the helices are held together by helically distributed phosphorus and nickel atoms to form a racemic network.In this paper, we reported a novel polyoxotungstate, H6[Ni3W4P4O28]·en·4H2O, which is the first 3-D racemic network that incorporates helical WO6-octahedral chains of different handedness as building blocks. The helices are held together by helically distributed phosphorus and nickel atoms, this steric orientation leads to the generation of a small square hole with the dimensions of 0.85 × 0.85 Å and an irregular pentagonal porous channel with the dimensions of 4.08 × 5.26 Å, in which some water and ethylenediamine molecules filled.
Keywords: Hydrothermal synthesis; Polyoxometalates; Helices; Self-assembly;

Two new layered isomorphic vanadates, [M(dpa)V3O8.5] (M = Cu2+ (1), Zn2+ (2); dpa = 2,2′-dipyridylamine) have been synthesized under hydrothermal reactions and electrochemical measurement shows that lithium ions are reversibly intercalated and deintercalated in vanadate 1.Two new isomorphic vanadates, [M(dpa)V3O8.5] (M = Cu2+ 1, Zn2+ 2; dpa = 2,2′-dipyridylamine) have been synthesized hydrothermally. X-ray crystal analysis reveals that vanadates 1 and 2 exhibit a layered structure constructed from {V3O8.5}2− layers inlaid with [M(dpa)]2+ subunits. The {V3O8.5}2− layers consist of ribbon-like chains of edge sharing {VO5} square pyramids bridged through {V2O7} fragments. Electrochemical measurement shows that lithium ions are reversibly intercalated and deintercalated in vanadate 1.
Keywords: Vanadate; Cu(II) complex; Zn(II) complex; Layered structure; Hydrothermal synthesis;

Synthesis, structure, and properties of two novel copper(II) complexes, [Cu(phen)(L)2]·6H2O and [Cu(phen)3]·(ClO4)2 by Feilong Hu; Xianhong Yin; Yan Mi; Shanshan Zhang; Weiqiang Luo; Yue Zhuang (1189-1192).
A novel Cu(II) complex with pyrazole and 1,10-phenanthroline ligands, which contain supramolecular (H2O)10 morphology. The hydrogen-bonding association leads to the formation of the infinite morphology of water molecules along the b-axis.Two novel copper(II) complexes, namely [Cu(phen)(L)2]·6H2O (1) and [Cu(phen)3]·(ClO4)2 (2) have been synthesized under mild condition (HL = 5-methyl-1H-pyrazole-3-carboxylic acid, phen = 1,10-phenanthroline). We report the structural evidence of discrete water decamer conformation in the solid state. These units are found to act as supramolecular glue in the aggregation of mononuclear copper(II) complex to give a three-dimensional network through hydrogen-bonding. The preliminary investigation on the thermal behavior and the anion exchange property of the complexes are presented.
Keywords: Copper(II) complex; Water clusters; Anion exchange; Crystal structure;

A novel cobalt complex with bulky anilido-iminato ligand was synthesized, structurally characterized by X-ray single-crystal diffraction, and its application as a catalyst for the addition polymerization of norbornene in the presence of methylaluminoxane was reported.A novel anilido-iminato cobalt complex [(L)Co(μ-Cl)2Li(THF)2] (1) (H(L) =  o-(2′,6′- i Pr2(C6H3)–NH)(C6H4)CH=N–(C6H3) Pr 2 i -2,6) was synthesized by the reaction of the lithium salt of H(L) with CoCl2 in THF in 57% yield, structurally characterized by NMR and X-ray single crystal diffraction, and its application as a catalyst for the addition polymerization of norbornene in the presence of methylaluminoxane (MAO) was reported.
Keywords: Cobalt complex; Anilido-iminato; Crystal structure; Addition polymerization;

This work reports X-ray crystal structure of a novel tricopper complex [(PPh3)2Cu]2[μ-o-OC6H4COO]2Cu (3). ESR, solid-state 31P MAS NMR, and UV–vis–NIR studies indicate that there exists Cu(I)Cu(II)Cu(I) units in 3.A novel neutral mixed-valence Cu(I)Cu(II)Cu(I) linear trinuclear copper metallomacrocycle [(PPh3)2Cu]2[μ-o-OC6H4COO]2Cu (3) has been synthesized and characterized. Compound 3 consists of two Cu(I) ions and one Cu(II) ion which are bridged by two salicylate (2) ligands, and the external copper(I) atoms are coordinated by four terminal triphenylphosphines. The essentially localized mixed-valence [Cu(I)Cu(II)Cu(I)] formulation for 3 was determined on the basis of X-ray crystallography, solid-state 31P MAS NMR, and ESR spectroscopy. The solid-state 31P MAS NMR spectra of 3 is reported, affording δ[P(2)] = −1.7 ppm with 1 J[Cu(I), P] = 1330 Hz and δ[P(1)] = −3.4 ppm with 1 J[Cu(I), P] = 1600 Hz. UV–vis–NIR spectral measurement demonstrates the Robin–Day class II behavior of the mixed-valence compound 3 with a weak copper–copper interaction.
Keywords: Crystal structure; 31P MAS NMR; ESR; Trinuclear copper complex;

Construction and photoluminescence properties of two novel zinc(II) and cadmium(II) benzyl-tetrazole coordination polymers by Biao Liu; Yong-Cai Qiu; Guo Peng; Li Ma; Li-Ming Jin; Jin-Biao Cai; Hong Deng (1200-1203).
Two new d10 coordination polymers, Zn(Beta)2 (1) and Cd2(Beta)3Cl(H2O) (2) (Hbeta = 5-benzyl-tetrazole) have been synthesized by the in situ [3 + 2] cycloaddition reaction of 5-benzylacetonitrile, sodium azide and MCl2 [M = Zn (1); M = Cd (2)] under hydrothermal condition. Complex 1 is a coordination polymer comprised of numerous mildly undulated two-dimensional (2D) layers with a (4, 4) topological network; while complex 2 is a 3D coordination framework constructed from the interconnection of various helical chains through cadmium–chlorine bridges.Two new d10 coordination polymers, Zn(Beta)2 (1) and Cd2(Beta)3Cl(H2O) (2) (Hbeta = 5-benzyl-tetrazole) have been synthesized by the in situ [3 + 2] cycloaddition reaction of 5-benzylacetonitrile, sodium azide and MCl2 [M = Zn (1); M = Cd (2)] under hydrothermal condition. Complex 1 is a coordination polymer comprised of numerous mildly undulated two-dimensional (2D) layers with a (4, 4) topological network; while complex 2 is a 3D coordination framework constructed from the interconnection of various helical chains through cadmium–chlorine bridges. Furthermore, the luminescence properties of two complexes have been investigated.
Keywords: Tetrazole; Helical chain; Fluorescence; Lifetime;

A highly novel dinickel complex: A hydrogen-bonded anti-skew carboxylate bridge and a 2D supramolecular structure by Neslihan Korkmaz; Aytaç Gürhan Gökçe; Stephen T. Astley; Muhittin Aygün; Demet Astley; Orhan Büyükgüngör (1204-1208).
The crystal structure of a novel dinickel amino acid Schiff base complex, [Ni2(C13H15O4N)2(H2O)5]·H2O and its 2D supramolecular structure, which arises from intermolecular O–H⋯O hydrogen bonds, is described.Reaction of the tridentate Schiff base ligands obtained from 2,4-dihydroxybenzaldehyde and either l-isoleucine or l-tert-leucine with Ni(NO3)2 in methanol/water solution in the presence of base afforded dinickel complexes. The crystal structure of the product derived from l-tert-leucine has been determined by X-ray crystallography. The octahedrally coordinated two Ni centers were found to be bridged by a single carboxylate group in an extremely unusual non-planar fashion. A 2D supramolecular structure, constructed by infinite hydrogen-bonded complex sheets parallel to the ab-plane of the unit cell, arises from intermolecular O–H⋯O hydrogen bonds.
Keywords: Dinickel complexes; Bridging carboxylate; Supramolecular structure; Tridentate Schiff base;

Synthesis of 1,1′-ferrocene bis(carboxypyrazole) compounds and displacement of the pyrazole ligands by Richard S. Herrick; Brenton R. Franklin; Christopher J. Ziegler; Anıl Çetin (1209-1211).
Reaction of 1,1′-ferrocenedicarbonyl chloride with pyrazole or 3,5-dimethyl pyrazole generates 1,1′-ferrocene bis(amide) compounds 1 and 2. Reaction with Mo(CO)4 (piperidine)2 led to pyrazole replacement by piperidine. The structure of 1 is reported.The reaction of 1,1′-ferrocenedicarbonyl chloride with pyrazole or 3,5-dimethyl pyrazole generates novel 1,1′-ferrocene bis(amide) compounds 1 and 2, respectively. The crystal structure of 1 shows that the pyrazole rings are essentially co-planar with each other and with the cyclopentadienyl rings. Attempts to use the complexes as a chelating ligand were unsuccessful. Instead, treatment of 1 or 2 with Mo(CO)4(pip)2, pip = piperidine, led to displacement of the pyrazole ligands and formation of the known amide compound, 1,1′-ferrocene bis carbonyl piperidine. Replacement of the pyrazole is ascribed to the weakness of the amide bond caused by the aromaticity of the pyrazole ring. Crystal data for C18H14FeN4O2 (1): monoclinic P2(1)/c, a  = 13.3907(18) Å, b  = 10.2112(14) Å, c  = 11.3082(16) Å, β  = 105.209(2)°, V  = 1492.1(4) Å3, Z  = 4.
Keywords: Crystal structure; Ferrocene; Pyrazole;

Near-IR sensitization of nanocrystalline TiO2 with a new ruthenium complex having a 2,6-bis(4-carboxyquinolin-2-yl)pyridine ligand by Nobuko Onozawa-Komatsuzaki; Masatoshi Yanagida; Takashi Funaki; Kazuyuki Kasuga; Kazuhiro Sayama; Hideki Sugihara (1212-1215).
A new ruthenium(II)–polypyridine complex (1) with a 2,6-bis(4-carboxyquinolin-2-yl)pyridine ligand was synthesized as a near-IR sensitizer for dye-sensitized solar cells (DSCs). DSCs sensitized with 1 showed a 35% incident photon-to-current conversion efficiency (IPCE) at 900 nm.A new ruthenium(II)–polypyridine complex (1) having a 2,6-bis(4-carboxyquinolin-2-yl)pyridine ligand was synthesized as a sensitizer for dye-sensitized solar cells (DSCs). This complex exhibited remarkable light-harvesting properties in the near-IR region. DSCs sensitized with 1 showed a 35% incident photon-to-current conversion efficiency (IPCE) at 900 nm.
Keywords: Ruthenium(II) complex; Dye-sensitized solar cell; Sensitizer;

Co-existence of heterometallic Zn2Er and ZnEr arrayed chromophores for the sensitization of near-infrared (NIR) luminescence by Tao Wei; Shunsheng Zhao; Weiyu Bi; Xingqiang Lü; Yani Hui; Jirong Song; Wai-Kwok Wong; Richard A. Jones (1216-1219).
Two co-crystallized heterometallic (both Zn2Ln and ZnLn array) complexes 1–2 were obtained. The results of sensitization and the energy transfer of the Zn(II) blocks for the NIR luminescence of the Er3+ ion show that the co-existence of different chromophores is a potentially effective way to the fine-tuning properties of NIR luminescence from Er3+ ion.With the Zn-Schiff-base [ZnL(Py)] from the simple Salen-type Schiff-base ligand H2L (H2L =  N,N′-bis(salicylidene)ethylene-1,2-diamine) as the precursor, two co-crystallized heterometallic (Zn2Ln and ZnLn array) complexes [Zn2Ln(L)2(Py)2(NO3)2]·[ZnLn(L)(Py)(NO3)3(H2O)]·NO3· m MeOH· n S (Ln = Er(1), S = CH3CN, m  = 2, n  = 1 or Gd(2), S = H2O, m  = 1, n  = 3) were obtained by the further reaction with Ln(NO3)3·6H2O, respectively. The result of their photophysical properties shows the intramolecular effective energy transfer has been demonstrated in the Zn2Er and ZnEr arrayed complex 1, and the co-existence of different chromophores should be a potentially new way to the fine-tuning properties of NIR luminescence from Er3+ ions.
Keywords: Co-existence of Zn2Er and ZnEr arrayed Schiff-base chromophores; Energy transfer; Fine-tuning of NIR luminescence;

Silver(I) coordination polymers self-assembled through methanolysis of pyrazinecarbonitrile: Structure and photoluminescence by Jong Won Shin; Ji Hoe Han; Bong Gon Kim; Sang Hun Jang; Sang Gyeong Lee; Kil Sik Min (1220-1223).
Novel supramolecular solids depending on the counteranion have been constructed from AgX ( X = CF 3 CO 2 - (1) and CF 3 SO 3 - (2)) with pyrazinecarbonitrile via the methanolysis of pyrazinecarbonitrile in the silver(I) methanolic solution. They are both one-dimensional ladder-like coordination polymers due to the π–π interactions. Both compounds display relatively strong photoluminescent behaviors.New supramolecular solids whose topologies depend on the counteranion, [Ag(MPCI)(CF3CO2)] (1) and [Ag2(MPCI)2(CH3OH)(CF3SO3)]CF3SO3 (2), have been prepared by the self-assembly of AgX ( X = CF 3 CO 2 - and CF 3 SO 3 - ) with pyrazinecarbonitrile (MPCI = methyl pyrazine-2-carboximidate). Both compounds are composed of methyl pyrazine-2-carboximidate (MPCI), in which the pyrazinecarbonitrile ligand is transformed into an MPCI by methanolysis in the presence of silver(I) ions. The coordination geometry around silver(I) ion in 1 is a distorted tetrahedral structure, while two silver(I) ions in the asymmetric unit of 2 are a seesaw-like structure and a square-planar one. Furthermore, 1 and 2 display one-dimensional ladder-like coordination polymers due to the π–π interactions. 1 shows a visible light emission ranging from violet to blue wavelengths, whereas 2 appears a weak visible emission at around 470 nm.
Keywords: Self-assembly; Silver; Pyrazine; Coordination chemistry; Offset π–π interaction; Photoluminescence;

A new mixed-ligand 3D MOF has been synthesized under hydrothermal conditions, which indicated a (6, 8)-connected honeycomb-like network topology. The results of X-ray crystallography revealed that the fumaric acid as the original reactant in situ converted into malate partly under the hydrothermal conditions.A crystalline 3D MOF {[Cu5(trz)2(mal)2(fma)(H2O)4]·2H2O} n (1) (trz = 1,2,4-triazolate, mal = malate, fma = fumarate) has been synthesized through hydrothermal method and characterized by X-ray crystallography, IR, elemental analysis and thermal gravimetric analysis. The crystal structure revealed that the fma was partly in situ converted into the mal under hydrothermal conditions and the compound was consisted of a 3D (6, 8)-connected honeycomb-like network. Furthermore, the catalytic performance of compound for the thermal decomposition of ammonium perchlorate (AP) was investigated by DSC. The experiment results indicated that the compound accelerated the decomposition of AP.
Keywords: Metal–organic framework; 1,2,4-Triazole; Fumarate; Malate; Catalytic thermodecomposition;

Two new 3D, sixfold interpenetrating coordination polymers of copper(I) having large pores of dimensions 35 × 21 Å2 and 38 × 19 Å2 were synthesized using flexible polydentate imine/pyridyl ligands.Two new coordination polymers [Cu(L1 )2] n (ClO4) n ·2nH2O (1), [Cu(L2 )2] n (ClO4) n ·2nH2O (2) of polydentate imine/pyridyl ligands, L1 and L2 with Cu(I) ion have been synthesized and characterized by single crystal X-ray diffraction studies, elemental analyses, IR′ UV–vis and NMR spectroscopy. They represent 3-dimensional, sixfold interpenetrating diamondoid network structures having large pores of dimension, 35 × 21 Å2 in 1 and 38 × 19 Å2 in 2, respectively.
Keywords: N-donor ligands; Coordination polymer; 3D polymer; Copper(I) complexes; Sixfold interpenetration; Diamondoid networks; Crystal structures;

A novel one-dimensional silver(I) complex, derived from 2-hydroxypyridine with Ag2O in an ammonia solution, have been prepared and structurally characterized. The complex show strong urease inhibitory activity.A novel one-dimensional silver(I) complex, derived from 2-hydroxypyridine with Ag2O in an ammonia solution, have been prepared and structurally characterized. Each Ag atom in the complex is three-coordinate in a T-shaped geometry with two phenolate O atoms and one pyridine N atom. Adjacent Ag atoms are linked by Ag–Ag interactions, forming an Ag4 unit. The Ag4 units are further linked by four phenolate O atoms, forming a one-dimensional chain running along the c axis. The fluorescence of the complex has been studied. The complex show strong urease inhibitory activity.
Keywords: Synthesis; Crystal structure; Silver complex; Fluorescence; Urease inhibition;

Metal–azido complexes, [M(N3)(PMe3)2(C–L)] {LH = 2-(2′)-thienyl pyridine; M = Pd, Pt} were treated with Me2C6H3–NCS to afford the corresponding tetrazole–thiolato complexes, trans-{M[SCN4(2,6-Me2C6H3)](PMe3)2(C–L)}.Pd(II)– and Pt(II)–azido complexes, [M(N3)(PMe3)2(C–L)] {LH = 2-(2′)-thienyl pyridine; M = Pd (1), Pt(2)}, which contain σ-bonded heterocycles (L), were treated with aryl isothiocyanate (Me2C6H3–NCS) to afford the corresponding Pd(II) and Pt(II) tetrazole–thiolato complexes, trans-{M[SCN4(2,6-Me2C6H3)](PMe3)2(C–L)} {M = Pd (3), Pt (4)}. Complexes 3 and 4 have a 1-D helical network formed by the intermolecular M⋯S van der Waals contacts.
Keywords: Azido; Tetrazole–thiolato; Van der Waals interactions; Palladium: platinum;

A chiral twofold interpenetrated diamond-like 3D In(III) coordination network with 4,4′,4″-phosphoryltribenzoate by Qiang Gao; Ming-Yan Wu; Lian Chen; Fei-Long Jiang; Mao-Chun Hong (1238-1241).
A novel In(III) coordination complex, [In(ptc)(H2O)] n (H3ptc = 4,4′,4″-phosphoryltribenzoic acid) (1), was synthesized under hydrothermal condition and characterized by single-crystal X-ray analysis, IR, X-ray powder diffraction (XRD), thermogravimetric analysis (TGA) and solid-state photoluminescence. Complex 1 crystallizes in a chiral P21 space group, In(III) ions are eight-coordinated and the ligand exhibits a novel and unique tetrahedral coordination mode. The complex shows intense blue emission at 435 nm with the excitation of 330 nm.A novel In(III) coordination complex, [In(ptc)(H2O)] n (H3ptc = 4,4′,4″-phosphoryltribenzoic acid) (1), was synthesized under hydrothermal condition and characterized by single-crystal X-ray analysis, IR, X-ray powder diffraction (XRD), thermogravimetric analysis (TGA) and solid-state photoluminescence. Complex 1 crystallizes in a chiral P21 space group, In(III) ions are eight-coordinated and the ligand exhibits a novel and unique tetrahedral coordination mode. The complex shows intense blue emission at 435 nm with the excitation of 330 nm.
Keywords: Crystal structure; Indium(III); 4,4′,4″-Phosphoryltribenzoic acid; Chiral;

A new high-dimensional architecture constructed from paradodecatungstate and [Cu(2-Hpzc)]2+ complexes by Yuan Chen; Jun Peng; Hai-jun Pang; Ai-xiang Tian; Peng-peng Zhang; Dan Chen; Min Zhu; Yonghui Wang; Huiyuan Ma (1242-1245).
A new compound with three-dimensional framework has been synthesized, which represents the first high-dimensional hybrids based on paradodecatungstate modified by [Cu(2-Hpzc)]2+ complexes.A new compound, H4{[Cu3(2-Hpzc)2(H2O)4](H2W12O42)}·13H2O (1) (2-Hpzc = 2-pyrazinecarboxylic acid), was synthesized in conventional condition and characterized by elemental analyses, IR spectroscopy, thermal gravimetric analysis, X-ray powder diffraction (XRPD) and single X-ray diffraction. In the structure of compound 1, each paradodecatungstate anion acts as a quadridentate ligand coordinating to four Cu2+ cations through its terminal oxygen atoms to form a two-dimensional (2D) layer. The infinite [Cu(2-Hpzc)]2+ chains connect adjacent layers forming a three-dimensional (3D) architecture. There exist two kinds of channels with sizes of ca. 5.737 × 4.628 Å2 and 9.104 × 8.640 Å2 along the b and c directions, respectively. The magnetic behavior of 1 exhibits antiferromagnetic interaction.
Keywords: Paradodecatungstate; 2-Pyrazinecarboxylic acid ligand; Magnetic property;

Room-temperature synthesis and luminescence properties of Eu3+/Tb3+-doped La(1,3,5-BTC)(H2O)6 by Kai Liu; Guang Jia; Yuhua Zheng; Yanhua Song; Mei Yang; Yeju Huang; Lihui Zhang; Hongpeng You (1246-1249).
La(1,3,5-BTC)(H2O)6 was prepared on a large scale at room temperature, which exhibits 1D ribbonlike strands and 3D network in the structure. Moreover, the La(1,3,5-BTC)(H2O)6 doped with Eu3+/Tb3+ can act as a suitable material for red and green emissions.The facile, rapid, and effective synthesis of coordination polymer La(1,3,5-BTC)(H2O)6 has been realized via direct precipitation at room temperature. It is found that the crystal structure is of monoclinic, space group Cc. The doped Eu3+ or Tb3+ ions samples have the same phase and exhibit red and green emissions under UV light excitation, respectively.
Keywords: Lanthanum; 1,3,5-BTC; Doping; Europium; Terbium; Photoluminescence;

Migration of 1,3-diazacyclohexane sub-rings in ring-contracted macrocyclic silver(I) complexes by Katsura Mochizuki; Yasunobu Ohgami; Akira Mochizuki; Kiyoharu Hayano (1250-1254).
Mononuclear and dinuclear silver(I) complexes with contracted macrocyclic ligands were synthesized ([AgLd]BPh4, 1, and [Ag2Lb](BPh4)2  · 2(DMF), 2). X-ray structural analysis revealed that in 1 the coordinated ligand Ld adopted a ring-contracted cis-form, with two 1,3-diazacyclohexane sub-rings positioned in a cis-configuration with respect to the macrocyclic ring center, while in 2 the ligand Lb adopted a ring-contracted trans-form.Mononuclear and dinuclear silver(I) complexes with contracted macrocyclic ligands were synthesized ([AgLd]BPh4, 1, and [Ag2Lb](BPh4)2  · 2(DMF), 2). X-ray structural analysis revealed that in 1 the coordinated ligand Ld adopted a ring-contracted cis-form, with two 1,3-diazacyclohexane sub-rings positioned in a cis-configuration with respect to the macrocyclic ring center, while in 2 the ligand Lb adopted a ring-contracted trans-form. 1H NMR and X-ray structural analysis revealed that the cis- and trans-forms are interconvertible depending on whether the complex is mononuclear or dinuclear and whether it is in crystalline form or in solution; i.e., the 1,3-diazacyclohexane sub-ring is capable of migration in ring-contracted macrocyclic silver(I) complexes.
Keywords: Synthesis; Silver(I) complexes; Ring-contracted macrocycle; X-ray structure; 1H NMR; 1,3-Diazacyclohexane;

A Cu2+ complex CuQ 2 has been synthesized and used as a colorimetric probe for the detection of cysteine and homocysteine in water through a displacement reaction. The experimental results suggest no interference by other amino acids to the detection of cysteine and homocysteine.The complex CuQ2 (HQ  = 8-hydroxy-7-(4-tolyldiazenyl)quinoline-5-sulfonic acid) has been synthesized and used as a colorimetric probe for the specific detection of cysteine and homocysteine in water through a displacement reaction. The detection can be performed either by the spectroscopy from the increased UV–vis absorbance at 498 nm or by the change of color from yellow to red upon addition of cysteine or homocysteine to the solution of the complex. The experimental results show no interference by other amino acids to the detection of cysteine and homocysteine.
Keywords: 8-Hydroxyquinoline; Colorimetric probe; Cysteine; Homocysteine;

A combination of NMR experiments and DFT calculations show that oxalate-diperoxovanadate(V) is seven-coordinated pentagonal bipyramidal in solid state, while six-coordinated pentagonal pyramidal in solution.In order to understand the geometric structure of oxalate-diperoxovanadate(V) K3[VO(O2)2(C2O4)]·H2O {abbr. bpV(ox)} in water, 51V and 13C NMR spectroscopy and density functional theory (DFT) calculations were employed to explore the difference with the solid structure of bpV(ox) from X-ray diffraction. It is suggested by the differences in the 51V and 13C isotropic chemical shifts between solid state and solution and verified by our DFT calculations that the geometry of bpV(ox) anion may undergo change upon dissolution. Besides, the 13C NMR spectra of the coordinated oxalate in bpV(ox) was first assigned with the help of DFT calculation. The combination of the NMR data and DFT calculations confirms that bpV(ox) is seven-coordinated pentagonal bipyramidal in solid, while it is six-coordinated pentagonal pyramidal when it dissolves in water. This study sheds some light on the coordination chemistry of peroxovanadium(V) complexes.
Keywords: NMR; DFT; Structure variation; Oxalate-oxodiperoxovanadate(V);