Inorganic Chemistry Communications (v.12, #3)

Contents List (iii-ix).

A new organic–inorganic hybrid compound based on Anderson-B polyoxomolybdates, (H2Pz)5[Al(OH)6Mo6O18]2(SO4)2  · 16H2O (1) (Pz = piperazine) was synthesized and reported for the first time. The analysis of the Hirshfeld surfaces of 1 makes us understand the type and nature of intermolecular interactions in the crystal in a visual manner.A new organic–inorganic hybrid compound based on Anderson-B polyoxomolybdates, (H2Pz)5[Al(OH)6Mo6O18]2(SO4)2  · 16H2O (1) (Pz = piperazine) was synthesized and characterized by elemental analysis, IR, and single-crystal X-ray diffraction. The anions in 1 are stacked into a layer in [2 0 0] plane by hydrogen bonds of water molecules and van der Waas force, and between the layers are the sulfate ions and piperazine ions. The hydroxyl hydrogen atoms of Anderson-B anion make the anion be hydrogen bond donor. And the sulfate anion is the hydrogen bond acceptor. The analysis of the Hirshfeld surfaces of 1 makes us understand the type and nature of intermolecular interactions in the crystal in a visual manner.
Keywords: Polyoxometalates; Anderson-B anion; Crystal structure; Hirshfeld surface analysis; Intermolecular interactions;

The action mechanism of vanadocene dichloride, Cp2VCl2 (Cp=η5-C5H5), has been investigated by interaction with apo-transferrin and albumin for its promising antitumor activities. Our ESR spectral studies clearly showed that VIV ion is readily transported from vanadocene chloride to transferrin, and the VIV ions are captured at the Fe(III) binding sites of transferrin as a VO2+ form.The action mechanism of vanadocene dichloride, Cp2VCl2 (Cp=η5-C5H5), has been investigated by interaction with apo-transferrin and albumin for its promising antitumor activities. Our ESR spectral studies clearly showed that VIV ion is readily transported from vanadocene chloride to transferrin, and the VIV ions are captured at the Fe(III) binding sites of transferrin as a VO2+ form. We also observed that some binuclear VO2+ complexes can efficiently transport the VO2+ ions to the apo-transferrin.
Keywords: Vanadocene dichloride; Apo-transferrin; ESR spectra; Anticancer activity;

A two-dimensional copper polymer constructed from rod-shaped ferromagnetic secondary building units by Zhao-Xi Wang; Ming-Xing Li; Min Shao; Hong-Ping Xiao (201-203).
Rod-shaped magnetic Cu3 SUBs with S  = 3/2 are bridged by end–end azide ligands to form a 2D coordination polymer. Magnetic investigation shows the ferromagnetic coupling between CuII ions and very weak antiferromagnetic interaction between clusters.On the basis of rod-shaped secondary building units (SBUs), a novel two-dimensional (2D) azide–copper polymer, [Cu3(N3)4(anol)2] (1; anol = aminoethanol), was synthesized and structurally characterized. Complex 1 is a neutral 2D coordination network consisting of trinuclear copper(II) clusters [Cu3(N3)4(anol)2] connected with the bridge of end-end (EE) azide group. Magnetic data analysis shows that a metamagnetic behavior is observed for 1 which is associated with significant ferromagnetic coupling intracluster over 4 K.
Keywords: Azide–copper; Crystal structure; Magnetic properties; SBUs;

Three unusual 3D 4d–4f coordination polymer, [AgLn(nic)2(ox)] · 2H2O [Ln = Eu (1); Dy (2); Ho (3)] [nic = nicotinate; ox = oxalate] were successfully synthesized. All three structures exhibit same 3D open heterometallic coordination frameworks that are constructed from rare zigzag lanthanide-ox-silver chains and nic linkers.By control of mixed organic ligands with different geometries, three unusual 4d–4f heterometallic coordination polymers, [AgLn(nic)2(ox)] · 2H2O [Ln = Eu (1); Dy (2); Ho (3)] [nic = nicotinate; ox = oxalate] have been synthesized under hydrothermal reaction. Three structures represent 3D open heterometallic coordination frameworks that are constructed from rare zigzag lanthanide-ox-silver chains and nic linkers. Furthermore, the luminescent property of complex 1 was discussed.
Keywords: Nicotinic acid; Ln(III)–Ag(I) heterometallic complexes; Isostructures; Luminescence;

One novel and unprecedented zinc coordination polymer with an unsymmetrical N,O-donor phenolic ligand, 3-n-butyl-2-(2-hydroxyphenyl)-3H-benzimidazole hydrochloride hydrate, has been prepared and characterized crystallographically, and the geometric structure and photoluminescent properties, investigated experimentally and theoretically by DFT calculation. The μ2-bridging ligands adopt uncommon and rare (O,N)-bridging poly(oligo)merization coordination mode, and not the common O-bridging poly(oligo)merization coordination mode, and lead to the unprecedented 1D polymer, which should be the first photoluminescent 1D polymer structure with such (O,N)-bridging poly(oligo)merization coordination mode, with N,O-donor phenolic ligands so far. The photoluminescent property is assigned to π → π ligand-to-ligand charge transfer transition (LLCT) in nature.One novel and unprecedented 1D zinc coordination polymer with an unsymmetrical N,O-donor phenolic ligand, [Zn(bpbm)2] n (1) (Hbpbm · HCl · H2O = 3-n-butyl-2-(2-hydroxyphenyl)-3H-benzimidazole hydrochloride hydrate) has been prepared and characterized crystallographically, and the geometric structure and photoluminescent properties, investigated experimentally and theoretically by DFT level. The deprotonated ligands, bpbm, as μ2-bridging, adopt uncommon (O,N)-bridging poly(oligo)merization coordination mode, and not the common O-bridging poly(oligo)merization coordination mode. The photoluminescent property is assigned to π → π ligand-to-ligand charge transfer transition (LLCT).
Keywords: Zinc(II) complex; Photoluminescence; Crystal structure; DFT; 1D polymer; 3-n-Butyl-2-(2-hydroxyphenyl)-3H-benzimidazole;

A crystalline 3D MOF with unique pentanuclear Cd(II)-cluster as SBU, [Cd5(H2O)4(ap)3(trz)4]n (1) (H2ap = adipic acid, Htrz = 1,2,4-triazole), was isolated by hydrothermal method, which exhibits strong trz-based solid-state luminescent emission. Interestingly, ap ligands in 1 were observed to play the important roles for both the aggregate of polynuclear motif and the extension of the infinite 3D framework.A crystalline 3D MOF with unique pentanuclear Cd(II)-cluster as SBU, [Cd5(H2O)4(ap)3(trz)4] n (1) (H2ap = adipic acid, Htrz = 1,2,4-triazole), was isolated by hydrothermal method, which exhibits strong Htrz-based luminescent emission. More interestingly, ap ligands in 1 were observed to play the important roles for both the aggregate of polynuclear motif and the extension of the infinite 3D framework.
Keywords: Metal-organic framework; Pentanuclear cluster; 1,2,4-Triazole; Secondary building unit;

Ionic liquid crystals from β-diketonyl containing pyridinium cations and tetrachlorozincate anions by M.J. Mayoral; P. Ovejero; J.A. Campo; J.V. Heras; E. Pinilla; M.R. Torres; M. Cano (214-218).
Bis{2-[3-(4-n-alkyloxyphenyl)propane-1,3-dion-1-yl]pyridinium}tetrachlorozincates [OOR(n)py]2[ZnCl4] have been synthesized and proved as ionic liquid crystals exhibiting thermotropic polymorphism and smectic enantiotropic behaviour. Layered structures, containing cationic and anionic sublayers, of the solid phase, a ordered smectic phase and a smectic A phase are established on the basis of the X-ray studies (crystal structure and variable temperature small-angles X-ray diffraction) to explain the polymorphism of those compounds.In this work, an approach towards ionic liquid crystals is strategically designed. A pyridine group has been attached to an 1,3-diketone containing an alkyloxyphenyl R substituent (R = C6H4OC n H2 n +1; n  = 10–18) and protonated with hydrochloric acid towards the formation of the chloride salts of 2-[3-(4-n-alkyloxyphenyl)propane-1,3-dion-1-yl]pyridinium cations [OOR(n)py]Cl (I), which have been proved to be non-mesomorphic. Reaction of these organic–inorganic compounds (I) with ZnCl2 yields to the ionic liquid crystals of the type bis{2-[3-(4-n-alkyloxyphenyl)propane-1,3-dion-1-yl]pyridinium}tetrachlorozincate [OOR(n)py]2[ZnCl4] (II).The crystalline structure of compounds [OOR(12)py]Cl and [OOR(10)py]2[ZnCl4] as representative examples of both kinds of salts have been solved and discussed. Both compounds exhibit layered structures containing cationic and anionic sublayers. In addition for the tetrachlorozincate salt [OOR(16)py]2[ZnCl4] structural relationships between the mesophases and the crystalline phase are proposed on the basis of the variable-temperature small-angle X-ray diffraction studies.
Keywords: Ionic liquid crystals; Ionic liquids; Tetrahalozincate;

Synthesis and characterization of a mixed-valence hexadecavanadate cluster with half-open framework by Lian Chen; Fei-Long Jiang; Ning Li; Chun-Feng Yan; Wen-Tao Xu; Mao-Chun Hong (219-222).
A new mixed-valence hexadecavanadate cluster compound, (Me2NH2)4[H6V16O42(SO4)] · 8H2O (1), has been synthesized via efficient method in organic media. The hollow cluster shell of 1, with a sulfate ion locating in its centre, exhibits four large eight-membered –O–V–O–V– rings on its surface, which makes the cluster into a half-open structure.A new mixed-valence hexadecavanadate cluster compound, (Me2NH2)4[H6V16O42(SO4)] · 8H2O (1), has been synthesized via an efficient method in organic media. The hollow cluster shell of 1, with a sulfate ion locating in its centre, exhibits four large eight-membered –O–V–O–V– rings on its surface, which makes the cluster into a half-open structure distinguished from the common hollow clusters built up with closed surfaces. The intense blue luminescence of 1 in solution state is scarcely reported for the polyoxometalate clusters.
Keywords: Vanadium; Hexadecavanadate; Polyoxometalate; Cluster structure;

A rare 2D coordination polymer of graphite-like structure extended by infinite silver–oxygen–silver bonds by Zhen-Jie Zhang; Hai-Yang Liu; Shi-Yuan Zhang; Wei Shi; Peng Cheng (223-226).
The reaction of AgNO3 and H3btb (H3btb = 1,2,3-benzenetricarboxylic acid) leads to the isolation of [Ag(μ2-H2O)(μ2-H2btb) · 1.5H2O] n (1), which crystallizes in the orthorhombic space group Fddd with a  = 11.436(2) Å, b  = 6.876(1) Å, c  = 58.837(1) Å, V  = 4626.5(2) Å3, Z  = 32. Silver ions are connected by strong Ag–Ag interactions and μ2-H2O bridges to form hexagonal Ag6 subunits, and are further assembled to a novel highly ordered 2D grid, which presents an interesting graphite-like 63 net.The reaction of AgNO3 and H3btb (H3btb = 1,2,3-benzenetricarboxylic acid) leads to the isolation of {[Ag(μ2-H2O)(μ2-H2btb)]} n  · 1.5nH2O (1), which crystallizes in the orthorhombic space group Fddd with a  = 11.436(2) Å, b  = 6.876(1) Å, c  = 58.837(1) Å, V  = 4626.5(2) Å3, Z  = 32. Silver ions are connected by both strong Ag⋯Ag interaction and μ2-H2O bridges to form hexagonal Ag6 subunits, and are further assembled into a high ordered 2D grid, presenting an interesting graphite-like 63 net. Both the fluorescence and the crystal transformation after dehydration are studied.
Keywords: Silver–oxygen–silver; 1,2,3-Benzenetricarboxylic acid; Graphite-like structure; 63 Net; Fluorescence;

Three novel tripodal ligands derived from diazafluorene and corresponding trinuclear Ru(II) complexes have been prepared. These complexes display MLCT absorption at 445 nm and emission at 578 nm. Cyclic voltammetry of these complexes are consistent with one Ru(II)-centered quasi-reversible oxidation and three ligand-centered reductionsThree tripodal ligands 2,2′,2″-tris[(4,5-diazafluoren-9-ylimino)phenoxyethyl]amine (L1), 1,3,5-tris[(4,5-diazafluoren-9-ylimino)phenoxymethyl]-2,4,6-trimethylbenzene (L2), 1,1′,1″-tris[(4,5-diazafluoren-9-ylimino)phenoxymethyl]-1″′-(p-tosyloxymethyl)-methane (L3), and corresponding Ru(II) complexes [(bpy)6L1–3(RuII)3](PF6)6 (Ru-L1–3) have been prepared. Cyclic voltammetry of the three complexes are consistent with one Ru(II)-centered quasi-reversible oxidation and three ligand-centered reductions. Photophysical behaviors are investigated by UV–Vis absorption and fluorescence spectrometry. The three complexes display metal-to-ligand charge transfer absorption at 445 nm and emission at 578 nm.
Keywords: Trinuclear Ru(II) Complex; Diazafluorene; Electrochemistry; UV–Vis Absorption; Emission;

A novel dinuclear rhenium(I) complex, {(bis[4-(2-pyridylmethyleneamino)phenyl]methane)[Re(CO)3Br]2}, 1 has been synthesized. The complex, 1 have been characterized by elemental analyses, IR and 1H NMR spectroscopic studies, and electrochemical behavior was measured. X-ray single-crystal structural analyses reveal that 1 is a dinuclear complex and two rhenium centers are separated by 10.5512(10) Å and the bis-bidentate ligand twists via a half-turn, around the metal–metal axis leading to a helical pitch size of about 23 Å.The synthesis, characterization, properties and crystal structure of {(bis[4-(2-pyridylmethyleneamino)phenyl]methane)[Re(CO)3Br]2} complex are reported. The 1H NMR data for this complex shows downfield shift of the bis-diimine ligand protons upon coordination to the Re center. The molecular structure of the dinuclear rhenium(I) complex exhibits distorted octahedral geometries around the each metal center with one Br and facial arrangement of three CO and a cis-bonded diimine ligands. The bis-diimine ligand, twists via a half-turn around the metal–metal axis. Electrochemical investigation reveals two oxidation waves and two irreversible reduction waves.
Keywords: Rhenium complex; Tetradentate diimine ligand; X-ray crystallography; Electrochemistry;

An unprecedented linear supramolecular manganese(III)-lithium(I) coordination polymer, [MnIIIL(OH)2LiI] n , has been prepared and characterized. Mn(III) atom of the title polymer is hexa-coordinated by the N2O2 donor atoms from the Salen-type ligand in the equatorial plane and two oxygen atoms from two μ-hydroxy groups in the axial positions. Li(I) atom is tetra-coordinated by two oxygen atoms from the Salen-type ligand and two oxygen atoms from two μ-hydroxy groups in the axial positions. This structure formed a one-dimensional infinite Mn(III)–O–Li(I) chain supramolecular structure by intermolecular O–H···O and O–H···Cl hydrogen bonds and π–π stacking of neighboring benzene rings.An unprecedented linear supramolecular manganese(III)-lithium(I) coordination polymer, [MnIIIL(OH)2LiI] n , has been prepared and structurally characterized. The polymer is a one-dimensional infinite Mn(III)–O–Li(I) chain supramolecular structure formed by intermolecular O–H···O and O–H···Cl hydrogen bonds and π–π stacking of neighboring benzene rings.
Keywords: Salen-type bisoxime ligand; Mn(III) polymer; Synthesis; Supramolecular structure;

Absolute emission quantum yield determination of self-assembled mesoporous titania films grafted with a luminescent zinc complex by Daniela Aiello; Flaviano Testa; Rosario Aiello; Luca Malfatti; Tongjit Kidchob; Plinio Innocenzi; Iolinda Aiello; Tonino Martino; Mauro Ghedini; Massimo La Deda (237-239).
A luminescent zinc complex was successfully added to mesostructured porous titania films through a grafting process. The resulting films show an intense blue-fluorescence increasing with functionalization time. The emission quantum yield of these newly synthesized films was quantitatively and accurately determined by measurements carried by an integrating sphere.A luminescent zinc complex was successfully incorporated to mesostructured porous titania films through a grafting process. The resulting films show an intense blue-emission increasing with functionalization time. The emission quantum yield of these newly synthesized films was quantitatively and accurately determined by measurements carried by an integrating sphere.
Keywords: Mesoporous materials; Thin films; Schiff base; Photoluminescence; Quantum yield;

A unique 1D luminescent CdII coordination chain in situ resulted from C–S bond cleavage by Hai-Bin Zhu; Jun-Feng Ji; Ya-Wen Zhang; Shao-Hua Gou (240-242).
A unique 1D Cd2+ coordination polymer has been in situ prepared via the C–S bond cleavage of BMSA ((BMSA  = 1H-Benzoimidazol-2-ylsulfanyl)acetic acid) under the hydrothermal condition.Hydrothermal reaction of CdI2 with BMSA (BMSA  = (1H-Benzoimidazol-2-ylsulfanyl)acetic acid) resulted in a unique 1D Cd2+ coordination polymer (1) with BMT (BMT  = benzoimidazole-2-thiol) as organic building blocks, which are generated from in situ C–S bond cleavage of BMSA. The polymer is composed of an inorganic skeleton chain [CdS2] n with BMT anchoring on both sides like wings. The free BMT ligand in (1) plays an important role in the construction of the 2D superamolecular structure via N–H⋯S hydrogen bonds. The luminescence emission spectrum of (1) features a broad luminescence with emission maxima at 390 nm when excited at 270 nm.
Keywords: Hydrothermal; Cadmium; Crystal structure; Luminescence;

A new one-dimensional 3d–4d Metal-based coordination polymers VO2(C7H3O4N)Ag(C10H8N2)·H2O has been synthesized hydrothermally and characterized by single crystal X-ray diffraction, Thermal gravimetric analysis and fluorescence spectroscopes. Infinite V–Ag double-chain ribbons are formed. Water moleculars link adjacent ribbons to form a undulated 2D supermolecular layer via hydrogen bonds.The hydrothermal synthesis of V2O5, AgNO3, pyridine-2,6-dicarboxylic acid (H2pdc) and 2,2′-bipyridine (bpy) in water at 160 °C for 4 days yields a novel 1D coordination polymer VO2(C7H3O4N)Ag(C10H8N2)·H2O (1). Each V center chelates to a tridentate ligand pdc2− and coordinates to two O atoms, while the square based pyramid conformation of Ag center consists of three O atoms and a bpy molecular. V and Ag polyhedra alternate by either carboxyl or oxo bridges to further form a unique 3d–4d heterometal-based 1D double-chain ribbon.
Keywords: Hydrothermal synthesis; Vanadium coordination polymer; Silver; Pyridine-2,6-dicarboxylic acid; 3d–4d heterometal;

Structure and chemical properties of a copper(II) hydrazido complex: [{Cu(HB(3,5-iPr2pz)3)}2(μ-NCOOEt)2] by Kiyoshi Fujisawa; Masaki Sugiyama; Yoshitaro Miyashita; Ken-ichi Okamoto (246-248).
The structure and oxidation state of the copper center in the novel copper(II) hydrazido(2−) complex [{Cu(L1)}2(μ-NCOOEt)2] were established by X-ray crystallography and several spectroscopic techniques.The novel copper(II) hydrazido(2−) complex ligated by hydrotris(pyrazolyl)borate was synthesized to obtain insight into the copper coordination chemistry in the presence of diazene and hydrazine ligands. The structure of [{Cu(L1)}2(μ-NCOOEt)2] was determined by X-ray crystallography, where L1 = hydrotris(3,5-diisopropyl-1-pyrazolyl)borate anion, and along with spectroscopic characterization, e.g. UV–Vis and ESR, prove the presence of copper(II) centers.
Keywords: Copper complex; Hydrotris(pyrazolyl)borate; Hydrazine; Crystal structure; Nitrogen compound;

N10 deca-coordinated environment for a Ba(II) complex with tetrapyridyl pendant-armed azamacrocyclic ligand by Luis Botana; Rufina Bastida; Alejandro Macías; Paulo Pérez-Lourido; Laura Valencia (249-251).
An interesting Ba(II) complex with a tetrapyridyl pendant-armed azamacrocyclic is reported. The X-ray crystal structure shows the metal ion coordinated by the 10 nitrogen donor atoms from the ligand, six of them from the macrocyclic framework and the remaining four nitrogen atoms from the pyridinic pendant-arms. The coordination geometry around the metal can be considered as a distorted bicapped cube. To the best of our knowledge, only two N10-coordinated Ba(II) complexes have been previously reported, and only one of them is a macrocyclic Ba(II) complex.An interesting Ba(II) complex with a tetrapyridyl pendant-armed azamacrocyclic is reported. The X-ray crystal structure shows the metal ion coordinated by the 10 nitrogen donor atoms from the ligand, six of them from the macrocyclic framework and the remaining four nitrogen atoms from the pyridinic pendant-arms. The coordination geometry around the metal can be considered as a distorted bicapped cube. To the best of our knowledge, only two N10-coordinated Ba(II) complexes have been previously reported, and only one of them is a macrocyclic Ba(II) complex.
Keywords: Barium(II); Azamacrocyclic ligand; Pendat-arms; X-ray crystal structure;

One new dinuclear multioxomolybdenum(VI) complex containing long Mo=O bands, with imidazole, [Mo2O6(imi)4], has been prepared and characterized crystallographically, and the geometric structure, electronic structure and spectroscopic properties, investigated experimentally and theoretically by using the density functional theory level (DFT and TDDFT). The rarely observed long Mo=O bonds (ca. 0.15 Å longer than other documents previously) are investigated in detail by orbital structure analysis for Mo=O groups. The existing elongation of Mo=O bonds in 1 may be helpful to the catalytic performance. Moreover the important electronic origins of the optical transitions are also mainly related to the Mo=O groups with ligand-to-metal charge transfer (LMCT) nature (Pterminal-oxo  →  d Mo) based on TDDFT calculation.One new dinuclear multioxomolybdenum(VI) complex containing long Mo=O bands with imidazole, [Mo2O6(imi)4] (1) (imi = imidazole), has been prepared and characterized, and the geometric structure, electronic structure and spectroscopic properties, investigated experimentally and theoretically. The rarely observed long Mo=O bonds in 1 (ca. 0.15 Å longer than documents previously) are analysed by orbital structure analysis. The electronic origins of the optical transitions are also mainly related to the Mo=O groups with ligand-to-metal charge transfer (LMCT) nature (Pterminal-oxo  →  d Mo).
Keywords: Molybdenum(VI); LMCT; Crystal structure; DFT; Spectroscopic properties; Imidazole;

Two 2-D homometallic and heterometallic Schiff-base complexes bridged by dicyanamide by Qian Shi; Lizi Sheng; Kefang Ma; Yunti Sun; Xiaoqing Cai; Ruowang Liu; Shun Wang (255-258).
Two Schiff-base complexes composed of homometallic and heterometallic dinuclear units, [Zn2(salpn)]2+ and [CuCd(salpn)]2+, have been prepared and characterized. The dinuclear second building units are connected by dicyanamide (dca) ligands, forming 2-D layer structure. Zinc(II) complex displayed structure-related photoluminescence properties in the solid state.Two Schiff-base complexes composed of homometallic and heterometallic dinuclear units, [Zn2(salpn)]2+ and [CuCd(salpn)]2+, have been prepared and characterized. The dinuclear second building units are connected by dicyanamide (dca) ligands, forming 2-D layer structure. Zinc(II) complex displayed structure-related photoluminescence properties in the solid state.
Keywords: Schiff-base compound; Homometallic and heterometallic complexes; Crystal structure; Thermal analysis; Fluorescent property;

A new inorganic–organic hybrid [ { Cu II ( pda ) ( H 2 O ) Cu 2 I ( bpy ) 3 } { GeMo 12 O 40 ] n · 2 n H 2 O was synthesized by hydrothermal method and its structure was determined by X-ray crystallography. The copper(I/II) complex located in 1 shows an unusual meso-helical chain structure, showing synergetic electrochemical and luminescence properties.A new inorganic–organic hybrid [ { Cu II ( pda ) ( H 2 O ) Cu 2 I ( bpy ) 3 } { GeMo 12 O 40 ] n · 2 n H 2 O (1), (pda = 1,2-propanediamine, bpy = 4,4′-bipyridine), was synthesized by hydrothermal method and its structure was determined by X-ray crystallography. The copper(I/II) complex located in 1 shows an unusual meso-helical chain structure. Different intertwined chains further connected with Keggin-type polyoxoanions by covalent Cu–Ot (terminal oxygen atom from polyanion) bonds to form 3D framework. The electrochemical and luminescence properties of 1 were investigated.
Keywords: Polyoxometalate; 3D framework; Meso-helical; Mixed-valence;

Two new isomeric complexes containing a well-resolved 1D water morph and (6, 3)-connected framework through hydrogen bonding interactions by Ping Liu; Guo-Ping Yang; Yao-Yu Wang; Gui-Lin Wen; Chun-Yan Guo; Qi-Zhen Shi (263-266).
Two complexes {[Cu(fum)(tpy)] · 5H2O} n (1) and [Cu2(fum)2(tpy)2] · 4H2O (2) have been synthesized upon the reaction of [Cu(fum)] with tpy (where fum = fumarate, tpy = 2,2′:6′,2″-terpyridine) in methanol–water solution. The crystal structure of 1 contains an unusual infinite 1D water cluster, notated as T4(2)10(2), which is directed by two independently H-bonded chiral helical water chains. And complex 2 shows a 14-membered macrocycle binuclear unit and a complicated (6, 3)-connected framework via H-bonded interactions.Two new isomeric complexes, namely {[Cu(fum)(tpy)] · 5H2O} n (1) and [Cu2(fum)2(tpy)2] · 4H2O (2), have been synthesized simultaneously from the reaction of Cu(fum) with tpy (where fum = fumarate, tpy = 2,2′:6′,2″-terpyridine) under mild condition. The crystal structures of complexes were determined by X-ray single-crystal diffraction. Complex 1 stabilizes in an unusual 1D water tape notated T4(2)10(2), which is directed by two chiral helical water chains; binuclear complex 2 represents a complicated (6, 3)-connected framework via supramolecular interactions. Additionally, complex 1 exhibits weak ferromagnetic behavior.
Keywords: Copper; Water chains; Hydrogen bond; Magnetic property;

Unsymmetrical exo-dentate IN ligand for further self-assembly with the Zn–Nd Salen-type Schiff-base ligands by Wei-Yu Bi; Xing-Qiang Lü; Wen-Li Chai; Tao Wei; Ji-Rong Song; Shun-Sheng Zhao; Wai-Kwok Wong (267-271).
The 2D layer polymeric [ZnL1Nd(IN)(NO3)2] n (1) (H2L1  =  N,N′-bis(3-methoxy-salicylidene)ethylene-1,2-diamine) and the discrete binuclear [ZnL2Nd(IN)(NO3)2(DMF] (2) (H2L2  =  N,N′-bis(3-methoxy-salicylidene)phenylene-1,2-diamine) complexes were obtained from the further self-assembly of unsymmetrical exo-dentate IN (IN  = isonicotinate) anion with the hetero-binuclear Zn–Nd Salen-type Schiff-base complexes as the building blocks. The change of linker flexibility of two Salen-type Schiff-base ligands (H2L1 and H2L2 ) resulted in the differences of structure and NIR luminescent property of their mixed-ligands complexes.With the hetero-binuclear Zn–Nd complex from the ethylene- or phenylene-linkered Salen-type Schiff-base ligand as the building block, further self-assembly of the unsymmetrical exo-dentate IN (IN  = isonicotinic) anion gave a 2D layer polymeric [ZnL1Nd(IN)(NO3)2] n (1) (H2L1  =  N,N′-bis(3-methoxy-salicylidene)ethylene-1,2-diamine) or a discrete binuclear [ZnL2Nd(IN)(NO3)2(DMF] (2) (H2L2  = N,N′-bis(3-methoxy-salicylidene)phenylene-1,2-diamine) complex, respectively. The change of linker flexibility of two Salen-type Schiff-base ligands (H2L1 and H2L2 ) resulted in the difference of structures and NIR luminescent properties of their mixed-ligands complexes.
Keywords: Unsymmetrical exo-dentate ligand; Zn–Nd Schiff-base complex; Self-assembly; Flexibility of linked groups; NIR luminescence;

A triarylmethane dye 1 detects CN from water and shows remarkable selectivity over other anions and dramatic color changes, in solution as well as when dyed. The pH stability of 1 in the range of 1.2–10.7 offers additional advantage in the sensing process under physiological conditions.A triarylmethane dye 1 detects CN from water and shows remarkable selectivity over other anions and dramatic color changes, in solution as well as when dyed. The pH stability of 1 in the range of 1.2–10.7 offers additional advantage in the sensing process under physiological conditions.
Keywords: Triarylmethane dye; ‘Naked-eye’ sensor; Highly selective sensor; Ready-to-use color-stable wool swatches; Reflectance studies; Cost-effective;

Synthesis, crystal structure, and thermal stability of a novel 3D cadmium carboxyphosphonate containing left-hand helical chains Cd3Cl2[(O3PCH2–N(H)C5H9–COO)2(H2O)2] · 4H2O by Jing Zhang; Jing Li; Zhen-Gang Sun; Rui-Nian Hua; Yan-Yu Zhu; Yan Zhao; Na Zhang; Lei Liu; Xin Lu; Wei-Nan Wang; Fei Tong (276-279).
A novel 3D cadmium carboxyphosphonate containing left-hand helical chains, Cd3Cl2[(O3PCH2–N(H)C5H9–COO)2(H2O)2] · 4H2O 1 has been synthesized by hydrothermal reaction at 120 °C and structurally characterized by single-crystal X-ray diffraction as well as with infrared spectroscopy, elemental analysis and thermogravimetric analysis. The hexanuclear clusters based on Cd(1)O4Cl2, Cd(2)O4Cl2, Cd(3)O6 and CPO3 polyhedra are interconnected through carboxyphosphonate ligands to form a 3D open-framework structure with channel system. It is interesting that a type of left-hand helical chain is formed by HL2− ligands bridging Cd3 ions running along the b-axis.A novel 3D cadmium carboxyphosphonate containing left-hand helical chains, Cd3Cl2[(O3PCH2–N(H)C5H9–COO)2(H2O)2] · 4H2O 1 has been synthesized by hydrothermal reaction at 120 °C and structurally characterized by single-crystal X-ray diffraction as well as with infrared spectroscopy, elemental analysis and thermogravimetric analysis. In compound 1, the hexanuclear clusters based on Cd(1)O4Cl2, Cd(2)O4Cl2, Cd(3)O6 and CPO3 polyhedra are interconnected through carboxyphosphonate ligands to form a 3D open-framework structure with channel system. The result of connections in this manner is the formation of 20- and 30-atom rings that are parallel to one another and run in the a-axis direction. It is interesting that a type of left-hand helical chain is formed by HL2− ligands bridging Cd3 ions running along the b-axis.