Inorganic Chemistry Communications (v.17, #C)

Contents List (iii-xiv).

Binuclear copper(II) complexes of Schiff base ligand derived from 1-phenyl-3-methyl-4-formylpyrazol-5-one and 1,3-diaminopropan-2-ol: Synthesis, structure and magnetic properties by Leonid D. Popov; Sergey I. Levchenkov; Igor N. Shcherbakov; Vladimir V. Lukov; Kyrill Y. Suponitsky; Victor A. Kogan (1-4).
Two novel binuclear heterobridged copper(II) Schiff base complexes of general formula [Cu2L(Pz)] (1) and [Cu2L(Az)(DMSO)]·DMSO (2) (where L = trianion of bis-azomethine derived from 1-phenyl-3-methyl-4-formylpyrazol-5-one and 1,3-diaminopropan-2-ol, Az = anion of 7-azaindole, Pz = pyrazolate anion) were synthesized and studied by IR spectroscopy and X-ray crystallography. Temperature dependence of magnetic susceptibility measurements show an antiferromagnetic coupling between two copper(II) ions in complex 1 (2  J = −  449) and ferromagnetic coupling in complex 2 (2  J  = 106 cm− 1).Two heterobridged copper(II) binuclear complexes are synthesizedDisplay Omitted► Two heterobridged copper(II) binuclear complexes are synthesized. ► Structural characterization involving single crystal XRD. ► Magneto-structural correlations are discussed. ► Exogenous bridge switch type of exchange interaction in heterobridged binuclear copper(II) complexes.
Keywords: Magnetic exchange interaction; Binuclear complex; Heterobridged complexes;

Hydrothermal reaction of a mixture of As, Mn, Se, en (en = ethylenediamine) and phen (phen = 1,10-phenanthroline) yields a novel inorganic–organic hybrid solid [Mn(phen)2]n[AsIII 2Se3(Se2)]n (1). It contains the one-dimensional (1D) 1[AsIII 2Se3(Se2)]2 − chains, in which Se2 2 − performs as bridging ligand to connect [As2Se5] (AsIII 2Se3(Se2)) units. The compound is a semiconductor with a band gap of 2.0 eV, and the variable-temperature magnetic susceptibility data suggests that the compound exhibits the antiferromagnetic interaction between the Mn2 + ions.A one-dimensional (1D) compound, [Mn(1,10′-phen)2]n[AsIII 2Se3(Se2)]n (1,10′-phen = 1,10′-phenanthroline), in which [Mn(1,10′-phen)2]2 + is incorporated into rare 1[AsIII 2Se3(Se2)]2 − chains, has been synthesized and characterized. It exhibits semiconducting properties with a band gap of Eg  = 2.03 eV, and the variable-temperature magnetic susceptibility data suggests the antiferromagnetic interaction between Mn2 + ions.Display Omitted► A novel compound, [Mn(1,10′-phen)2]n[AsIII 2Se3(Se2)]n 1, has been synthesized. ► Compound 1 has the rare 1 ∞[AsIII 2Se3(Se2)]2 − chains. ► Compound 1 exhibits semiconducting properties. ► Compound 1 shows the antiferromagnetic interaction between Mn2 + ions.
Keywords: Chalcogenidoarsenates; Hydrothermal reaction; Polychalcogenide ligands; Bridging ligand; Semiconductor; Antiferromagnetic;

A new metal–organic framework based on hexanuclear copper units, Cu63-O)(μ3-OH)(pz)6(btc) (pz = pyrazolate, btc = 1,3,5-benzenetricarboxylate) 1, has been prepared by the hydrothermal reaction of Cu2 + ions, Hpz and H3btc ligands in a methanolic solution. The hexanuclear copper building unit in 1 is composed of two triangular Cu3O(H)(pz)3 units bridged by carboxyl groups, in which each Cu center is coordinatively unsaturated with open coordination sites. The photocatalytic investigation indicates that compound 1 exhibits a higher photocatalytic activity for the degradation of Rhodamine B.A new MOF based on hexanuclear copper units was synthesized and structurally characterized as a (3,3)-connected network.Display Omitted► A new MOF based on hexanuclear copper units was synthesized and characterized. ► The first example of MOFs based on Cu6 unit constructed by two Cu33-O) units. ► Each copper center is coordinatively unsaturated with open coordination sites. ► Compound 1 exhibits higher photocatalytic activity for the degradation of RhB.
Keywords: Metal–organic framework; Copper cluster; Unsaturated metal center; Structure; Photocatalytic activity;

The reaction of Cu(NO3)2·3H2O/Zn(NO3)2·6H2O and D-3-(4-Pyridyl)-alanine (Hpyala) without or with 4,4′-bipyridine (bpy) leads to the generation of two new coordination polymers, [Cu(pyala)2]·H2O (1) and [Zn(4-pyridylacrylate)2]·H2O (2). Interestingly, the 4-pyridyacrylate ligand was derived from the in situ deaminization of the D-3-(4-Pyridyl)-alanine under the hydrothermal conditions. Single-crystal X-ray diffraction studies indicate that 1 exhibits a one-dimensional (1D) chiral chain structure; 2 exhibits 3D framework with 5-fold interpenetrated diamondoid topology, which contains open channels occupied by the lattice water molecules.The reaction of Cu(NO3)2·3H2O/Zn(NO3)2·6H2O and D-3-(4-Pyridyl)-alanine (Hpyala) without or with 4,4’-bipyridine (bpy) leads to the generation of two new coordination polymers, [Cu(pyala)2]·H2O and [Zn(4-pyridylacrylate)2]·H2O. Interestingly, the 4-pyridyacrylate ligand was derived from the in situ deaminization of the D-3-(4-Pyridyl)-alanine under the hydrothermal conditions.Display Omitted► [Cu(pyala)2]·H2O(1) and [Zn(4-pyridylacrylate)2]·H2O(2) have been synthesized. ► 4-pyridylacrylate was in situ generated from D-3-(4-Pyridyl)-alanine. ► 1 exhibits a one-dimensional chiral chain structure. ► 2 is a 3D framework with 5-fold interpenetrated diamondoid topology.
Keywords: Coordination polymer; Chirality; Hydrothermal synthesis; Crystal structure; 5-fold interpenetrated; In situ deaminization;

NIR luminescence of 2-(2′-hydroxyphenyl)benzimidazole lanthanide (Ln=Nd and Yb) complexes by Peng Chen; Quan Li; Shuo Chen; Pengfei Yan; Yan Wang; Guangming Li (17-20).
Reactions of 2-(2′-hydroxyphenyl)benzimidazole (HL) with Nd(NO3)3  ⋅ 6H2O and YbCl3  ⋅ 6H2O affords two lanthanide complexes [H2L]2[Nd(HL)2(NO3)4]2  ⋅ 2CH3OH   ⋅ 2H2O (1) and [H2L][Yb(HL)2Cl4] ⋅ 2CH3OH (2), respectively. X-ray crystallographic analysis reveals that the two crystallographically distinct Nd3+ ions are ten-coordinated to two O atoms from two ligands and eight O atoms from four bidentate nitrate groups in 1. In the case of 2, the crystallographically distinct Yb3+ ion is hexa-coordinated to four Cl ions and two O atoms in an octahedral geometry. Structural analysis indicates the importance of H-bondings and π–π stacking in the construction of 1 and 2. Complexes 1 and 2 exhibit essential NIR luminescence of Nd3+ and Yb3+ ions, respectively.Two unique 2-(2′-hydroxyphenyl)benzimidazole lanthanide complexes [H2L]2[Nd(HL)2(NO3)4]2  ⋅ 2CH3OH   ⋅ 2H2O (1) and [H2L][Yb(HL)2Cl4] ⋅ 2CH3OH (2) have been isolated. The NIR luminescence of Nd3+ and Yb3+ ions for 1 and 2 are investigated, respectively.Display Omitted► Two 2-(2′-hydroxyphenyl)benzimidazole complexes have been prepared. ► Weak interaction dominates the structural construction. ► The ligand promotes the NIR luminescence of Nd3+ and Yb3+ ions.
Keywords: NIR; Lanthanide complex; Structure; 2-(2′-Hydroxyphenyl)benzimidazole;

A novel three-dimensional copper molybdate [CuI(PCI)Mo2 VO5] (1) (PCI = pyridine-4-carboxylic ion) has been synthesized under hydrothermal conditions and characterized by elemental analysis, IR, TG, XPS and single-crystal X-ray diffraction analysis. In compound 1, the {Mo2 VO5N}n dimeric chains alternately connect to copper chains via corner-sharing mode to form the bimetallic{CuIMo2 VO5N}n layer. These adjacent layers are linked by PCI ligands to generate a 3D framework. Interestingly, the PCI ligand is generated from the 1,3-bis(4-pyridyl) propane precursor via catalytic oxidation of polyoxomolybdate and copper cation. The electrochemical and electrocatalysis behavior of compound 1 have been studied in detail.The {Mo2 VO5N}n dimeric chains alternately connect to copper chains via corner-sharing mode to form the bimetallic{CuIMo2 VO5N}n layer. These adjacent layers are linked by PCI ligands to generate 3D framework.Display Omitted► The {Mo2 VO5N}n chains connect to copper chains to form the{CuIMo2 VO5N}n layer. ► The adjacent {CuIMo2 VO5N}n layers are linked by PCI to generate 3D network. ► The PCI is generated from the 1,3-bis(4-pyridyl) propane via in-situ generation. ► 1-CPE displays unique redox properties and good electrocatalytic activity.
Keywords: in-situ generation; PCI; Polyoxomolybdate;

A novel iridium(III) alkoxide dimeric complex containing 2-(4,6-difluorophenyl)pyridyl cyclometalating ligand was synthesized and characterized by IR, 1H-NMR and X-ray crystallographic methods. Aside from its novel structure and mechanistic implications as intermediate during the formation of homoleptic or heteroleptic Ir(III) complexes, it is interesting to note that this complex shows significant photoluminescence.An iridium(III) alkoxide dimeric complex containing 2-(4,6-difluorophenyl)pyridyl cyclometalating ligand was synthesized and characterized, which is significant in view of its novel structure and mechanistic implications for the formation of Ir(III) complexes. Additionally, it is interesting to note that this complex shows significant photoluminescence, similar to those for related Ir(III) amidate complexes.Display Omitted► Ir(III) 2-(4,6-difluorophenyl)pyridyl complexes. ► Ir(III) alkoxide complexes. ► Mechanistically relevant Ir(III) intermediates. ► Photoluminescence of Ir(III) alkoxide complexes.
Keywords: Iridium alkoxide complex; X-ray crystallographic structure; Photoluminescence; 2-(4,6-difluorophenyl)pyridine;

A new 3-fold interpenetrated metal-organic framework (MOF) based on trinuclear zinc(II) clusters as secondary building unit (SBU) by Yong-Liang Liu; Ke-Fen Yue; Bing-Hui Shan; Li-Li Xu; Cheng-Jun Wang; Yao-Yu Wang (30-33).
A new metal-organic framework (MOF), [Zn3(4,4’-ADB)3(BIB)2]n (1) has been synthesized based on mixed bridging ligands BIB and 4,4’-ADB (BIB = 1,4-bis(2-methyl-imidazol-1-yl) butane, 4,4’-ADB = azobenzene-4,4’-dicarboxylica acid). This MOF is a 3D structure with trinuclear zinc(II) clusters as SBU. The trinuclear zinc (II) clusters of line style feature zincs in two tetrahedral and one octahedral coordination environments. The MOF exhibits a 3-fold interpenetrated framework with 36·418·53·6 topology, which reduces the effective void but stabilizes the compound.One new coordination polymer [Zn3(4,4’-ADB)3(BIB)2]n (1) has been synthesized. It exhibits a 3D structure with trinuclear zinc(II) clusters of line style as the secondary building unit (SBU), and displays a 3-fold interpenetrated framework.Display Omitted► [Zn3(4,4’-ADB)3(BIB)2]n (1) has been synthesized. ► It is a new 3-fold interpenetrated framework. ► It contains two types of Zn atoms that trinuclear zinc(II) cluster as SBU.
Keywords: Metal-organic framework (MOF); The secondary building unit (SBU); Interpenetration;

Synthesis, structural characterization and catalytic activity of two N-heterocyclic carbene–phosphine palladium(II) complexes by Chen Xu; Xin-Qi Hao; Zhen Li; Xin-Ming Dong; Lu-Meng Duan; Zhi-Qiang Wang; Bao-Ming Ji; Mao-Ping Song (34-37).
Two new N-heterocyclic carbene (NHC)-phosphine palladium(II) complexes Pd(IMeo)PPh3I2 1 and Pd(IMeo) P(C6H4-p-Me)3I2 2 (IMeo = 1,3-di-4-methoxyphenyl- imidazolin-2-ylidene) have been easily prepared from the reaction of the corresponding iodide-bridged NHC dimer with phosphine ligands in high yields. Complexes 1 and 2 were characterized by elemental analysis, IR, 1H NMR, ESI-MS and single-crystal X-ray analysis. Complex 1 adopts a trans geometry in the solid state, while 2 is cis. The common features of the structures of these complexes are intermolecular C―H⋯I and C―H⋯O hydrogen bonds. These complexes were found to be efficient catalysts for the Suzuki reaction of aryl bromides.Two new N-heterocyclic carbene–phosphine palladium(II) complexes 1 and 2 have been synthesized. Complex 1 adopts a trans geometry in the solid state, while 2 is cis. These complexes were found to be efficient catalysts for the Suzuki reaction of aryl bromides.Display Omitted► Two NHC-phosphine palladium(II) complexes have been synthesized. ► Complex 1 adopts a trans geometry in the solid state, while 2 is cis. ► The two complexes were effective catalysts for the Suzuki reaction.
Keywords: N-heterocyclic carbene; Phosphine; Palladium(II) complex; Crystal structure; Suzuki reaction;

Silver atoms and strongly interlinking α-metatungstate units ensure the 3D structure of (NH4)5[Ag5(L)2(H2O)8(H2W12O40)]·H2O (L = pyridine-3,5-dicarboxylate dianion), which has been synthesized in aqueous solution and characterized by the normal physical methods as well as the single-crystal X-ray diffraction. This compound represents the first example that the α-metatungstate cluster as the structural motif is linked by transition metal complexes to yield unprecedented 3D framework with the highest eleven-connected number.Worth mentioning here that the {W12}6− cluster is decorated by eleven AgI ions, which represents the highest connected number of the α-metatungstate POMs to date.Display Omitted► The [H2W12O40]6− cluster is coordinate bonded to eleven AgI ions. ► Only by Ag(1) ions and [H2W12O40]6 − clusters form the 3D framework. ► Only by Ag(2) ions and [H2W12O40]6 − units form the 2D layers. ► The whole structure contains two motifs, a 3D framework and a 2D layer.
Keywords: α-Metatungstate polyoxometalate; Transition metal complexes; Silver; Multidimensional framework;

A new tetradentate ligand N,N′-Bis (1-butyl-benzimidazol-2-yl-methyl)-hexane-1,6-dicarboxamide (b-GBSA) has been utilized to synthesize mononuclear copper (II) complexes with inner sphere anionic ligands like NO3 , Br and Cl. Two of the complexes [Cu(L)NO3]NO3 (1) and [Cu(L)Br]Br (2) have been structurally characterized. The geometry of copper (II) in (1) is a distorted octahedral with NO3 anion acting as a bidentate ligand, while for (2) the geometry is found to be a near square pyramidal. The complexes carry out the oxidation of substituted amino phenols in the presence of molecular oxygen. The oxidation gets blocked at the dihydrophenoxazinone stage for 2-amino-5-methyl phenol, and to o-quinone for 2-amino-4-tertiary butyl phenol, quite like the enzyme phenoxazinone synthase.The enzyme catalyzed oxidation of substituted amino phenol is found to be blocked at various intermediate stages by using substituted amino phenols, and thus does not form phenoxazinone. The present series of copper (II) complexes catalyze the oxidation of 2amino-5-methyl phenol to dihydrophenoxazinone and oxidation of 2-amino-4-tertbutylphenol to o-quinone thus mimics the phenoxazinone synthase activity.Display Omitted► A new ligand N,N′-Bis (1-butyl-benzimidazol-2-yl-methyl)-hexane-1,6-dicarboxamide has been synthesized and characterized. ► Copper (II) complexes of ligand have been characterized by X-ray crystallography, EPR, CV, IR and UV–visible. ► Complex 1 is tetragonally distorted octahedral. ► Complex 2 is distorted square pyramidal. ► The complexes carry out the oxidation of substituted amino phenols and mimics the phenoxazinone synthase activity.
Keywords: Benzimidazole diamides; Copper (II) complexes; Substituted amino phenols; Phenoxazinone synthase;

A novel chiral copper-based complex constructed from chiral ligand, namely [Cu(L)(H2O)]·H2O (1) (L = (S)-3-phenyl-2-(pyrazine-2-carboxamido) propanoic acid). Complex 1 was prepared through solvothermal reactions and characterized by single-crystal X-ray diffraction. Complex 1 crystallizes in the tetragonal system with non-centrosymmetric polar space group P43 and affords one-dimensional (1D) chiral helical chain. Ferroelectric and magnetic studies reveal that 1 shows both ferroelectric and weak ferromagnetic properties.A novel chiral copper-based complex crystallizes in the tetragonal system with non-centrosymmetric polar space group P43 and affords one-dimensional (1D) chiral helical chain. Ferroelectric and magnetic studies reveal that 1 shows both ferroelectric and weak ferromagnetic properties.Display Omitted► Crystallizes in the tetragonal system with non-centrosymmetric polar space group P43 and affords one-dimensional (1D) chiral helical chain. ► The adjacent helical chains are linked by intermolecular hydrogen bonds, generating a 3D supermolecular network. ► Ferroelectric and magnetic measurements show both ferroelectric and weak ferromagnetic properties.
Keywords: Copper; One-dimensional; Chiral; Ferroelectric; Ferromagnetic;

A metal–organic framework based on Wells–Dawson polyoxometalates [As2W18O62]6 − template by Yuan Yang; Shuxia Liu; Congcong Li; Shujun Li; Guojian Ren; Feng Wei; Qun Tang (54-57).
A metal–organic framework based on Wells–Dawson polyoxometalate [As2W18O62]6 −, Co2(bpy)3(ox)(As2W18O62)·2(H2bpy)·2H2O (1) (bpy = 4,4′-bipyridine, ox = oxalate), has been synthesized hydrothermally by reacting Co(NO3)2, 4,4′-bipyridine, oxalate and K6As2W18O62. Single-crystal X-ray diffraction reveals that compound 1 contains a 3D cationic host framework composed of oxalate-bridged binuclear secondary building unit and 4,4′-bipyridine linkers. The channels of the 3D host framework are occupied by Wells–Dawson [As2W18O62]6 − templates. Thermogravimetric analysis shows the host framework keeps high thermal stability up to 450 °C. Furthermore, the electrochemistry property of 1 has been studied. The result indicates 1 has good electrocatalytic activity toward the reduction of nitrite.A 3D metal-framework is constructed by Wells–Dawson polyoxometalates [As2W18O62]6 − template. Compound 1 contains 3D cationic host framework constructed from oxalate-bridged binuclear secondary building unit and 4,4′-bipyridine linkers, and the channel of which are occupied by Wells–Dawson [As2W18O62]6 − templateDisplay Omitted► Polyoxometalates-templated metal–organic framework have attracted extensive interest due to their intriguing structure topologies and application in catalyst and sorption. ► We again confirmed that POMs is effective template to construct MOFs and the pore can be controlled by the choice of suitable POM. ► TG analysis exhibits that POMs can improve the thermal stability of the host framework. ► Compound 1 shows good electrocatalytic activity towards the reduction of nitrite.
Keywords: Metal–organic framework; Polyoxometalates; Electrochemical;

Dihydropyrimidinones (DHPM's) have been prepared by one-pot condensation of aldehydes, urea and 1,3-dicarbonyl compounds in presence of covalently anchored nickel complex on silica as catalyst in microwave under solvent-free conditions. The prepared catalyst was characterized by elemental analysis, BET surface area, atomic absorption spectroscopy (AAS), FT-IR spectroscopy and 13C CPMAS spectral studies. This method in comparison to previously reported methods offers high yields, eliminates the use of organic solvents, reduces reaction time from several hours to few minutes and also the catalyst can be reused without appreciable loss in catalytic activity.Silica immobilized nickel complex has been found to be efficient and recyclable catalyst for the synthesis of bioactive dihydropyrimidinones under solvent-free and microwave irradiation.Display Omitted► Synthesis of silica immobilized nickel complex. ► Characterization of catalyst by CHN, BET,AAS, FTIR and 13C CPMAS NMR. ► Greener method for synthesis of DHPM's under microwave radiations and solvent free condition. ► Recyclability of catalyst without significant decrease in catalytic activity.
Keywords: Biginelli reaction; Dihydropyrimidinones; Microwave; Nickel complex; Silica; One-pot;

Synthesis, structure, and luminescent property of a novel cadmium (II) carboxyphosphonate with a 2D layered structure using 1,4-benzenedicarboxylic acid as second linker by Cheng-Qi Jiao; Cui-Ying Huang; Zhen-Gang Sun; Kai Chen; Cheng-Lin Wang; Chao Li; Yan-Yu Zhu; Hui Tian; Shou-Hui Sun; Wei Chu; Ming-Jing Zheng (64-67).
By using the (2-carboxypiperidyl)-N-methylenephosphonic acid as the phosphonate ligand and 1,4-benzenedicarboxylic acid as the second metal linker, a novel cadmium(II) carboxyphosphonate with a 2D layered structure, namely, [Cd2(HL)(bdc)] (1) (H3L═H2O3PCH2―NC5H9―COOH, H2bdc═HOOCC6H4COOH) has been synthesized under hydrothermal conditions. In compound 1, each Cd(II) atoms are octahedrally coordinated [Cd(1)O6, Cd(2)O6]. These cadmium octahedra form a 1D double chain along the b-axis through edge- and corner-sharing, and such chains are further interlinked by the bdc2 − anions into a 2D layer in the bc-plane. The luminescent property of compound 1 has also been studied.A novel cadmium(II) carboxyphosphonate with a 2D layered structure, namely, [Cd2(HL)(bdc)] (1) (H3L = H2O3PCH2―NC5H9―COOH, H2bdc = HOOCC6H4COOH) has been synthesized under hydrothermal conditions. Furthermore, compound 1 shows favorable luminescent property at room temperature.Display Omitted► A novel cadmium(II) carboxyphosphonate with a 2D layered structure has been synthesized under hydrothermal conditions. ► Compound 1 is the first example of cadmium phosphonates with 2D layered structure using H2O3PCH2NC5H9COOH (H3L) as ligand. ► The luminescent analysis indicates that the use of H2bdc may be an effective way to prepare blue luminescent materials.
Keywords: Metal phosphonates; Crystal structure; Cadmium; Luminescent property;

One 2D Ni(II)-based compound showing diamagnetic-paramagnetic transition by Wen-yuan Xu; Xiao-zhao Tian; Gong-ming Sun; Yu-mei Song; Zi-zun Yuan; Zhen-wei Liao; Hai-xiao Huang; Ming-biao Luo; Shu-juan Liu; Feng Luo (68-70).
The title complex, [Ni(OPDA)Cl2]n (1, OPDA =  o-Phenylenediamine), is synthesized hydrothermally. The single crystal X-ray diffraction reveals that compound 1 is a 2D honeycomb net, where the Ni(II) ions are bridged by both single and double Cl- bridges. Magnetic studies of it disclose an interesting diamagnetic-paramagnetic transition.We present here a novel Ni(П) compound based on Cl- and OPDA ligands. Through both single and double Cl- bridges compound 1 displays a 2D inorganic NiCl2 net. Highlighted here is a paramagnetic-diamagnetic transition and its possibly structural change.Display Omitted► Presented here is a 2D inorganic NiCl2 net. ► It shows a diamagnetic-to-paramagnetic transition. ► Possible structural change is deduced.
Keywords: Ni(II) compound; OPDA; Inorganic NiCl2 net; Diamagnetic-paramagnetic transition;

A novel 3D polyoxometalate-linked polypseudo-rotaxane framework by using semi-rigid bis(triazole) ligand by Xiuli Wang; Xiaojing Liu; Aixiang Tian; Jun Ying; Hongyan Lin; Guocheng Liu; Juwen Zhang; Dan Zhao (71-74).
A novel 3D polyoxometalate-linked polypseudo-rotaxane framework, [Cu(L)2(HPWVI 10WV 2O40)][Cu(L)(H2O)4]⋅4H2O (1) (L  = 4,4′-bis(1,2,4-triazol-1-ylmethyl)biphenyl), was synthesized under hydrothermal conditions. Compound 1 contains a 2D grid-like sheet, which is constructed from bi-nuclear [Cu2 L 2]4 + cycles and Keggin anion linkages. The 1D polymeric [CuL(H2O)4]2 + chains penetrate the 2D sheets at an inclined angle to generate an interesting 3D polypseudo-rotaxane architecture.The title compound contains a 2D grid-like sheet, which is constructed from bi-nuclear [Cu2 L 2]4 + cycles and Keggin anion linkages. The 1D polymeric [CuL(H2O)4]2 + chains penetrate the 2D sheets at an inclined angle to generate an interesting 3D polypseudo-rotaxane architecture.Display Omitted► A novel 3D POM-linked polypseudo-rotaxane framework was obtained. ► [CuL(H2O)4]2 + chains penetrate the 2D POM-based sheets constructing a 3D framework. ► Title compound shows a good electrocatalytic activity toward reduction of nitrite.
Keywords: Keggin polyoxometalate; Hydrothermal synthesis; Semi-rigid bis(triazole) ligand; Polypseudo-rotaxane;

A novel sandwich-type polytungstosilicate K6H3[Nb2K(H2O)4(A-α-SiW9O34)2]·23H2O (1) has been prepared by reaction of K7HNb6O19·13H2O with Na10[A-α-SiW9O34]·23H2O in the presence of H2O2 under acidic medium and structurally characterized by elemental analysis, IR spectra, UV spectra and single-crystal X-ray diffraction. 1 consists of two trivacant Keggin [A-α-SiW9O34]10− moieties linked via a V-shaped {Nb2K} group resulting in a diniobium-inserted sandwich-type structure and represents a novel diniobium-inserted sandwich-type tungstosilicate. The photocatalytic measurement illustrates that 1 can effectively accelerate the photodegradation of rhodamine-B.The novel diniobium-inserted sandwich-type tungstosilicate K6H3[Nb2K(H2O)4(A-α-SiW9O34)2]·23H2O has been prepared by reaction of K7HNb6O19·13H2O with Na10[A-α- SiW9O34]·23H2O in the presence of H2O2 under acidic medium and structurally characterized.Display Omitted► The hybrid represents the novel diniobium-inserted sandwich-type polytungstosilicate. ► Prepared in the presence of H2O2 under acidic medium. ► Two [A-α-SiW9O34]10− subunits linked via a V-shaped {Nb2K} group. ► Can effectively accelerate the photodegradation of rhodamine-B.
Keywords: Polyoxometalate; Sandwich-type structure; Niobium; Photocatalyst;

A novel organic–inorganic hybrid hexa-NiII sandwiched germanotungstate [enH2]2[Ni(en)2]2{[Ni6(en)2(H2O)2] [B-α-GeW9O34]2}·14H2O (1) has been hydrothermally synthesized and structurally characterized. 1 consists of a hexa-nickel sandwiched polyoxoanion {[Ni6(en)2(H2O)2][B-α-GeW9O34]2}8 −, two discrete [Ni(en)2]2 + cations, two free diprotonated [enH2]2 + cations and fourteen lattice water molecules. Notably, the sandwich-type polyoxoanion {[Ni6(en)2(H2O)2][B-α-GeW9O34]2}8 − is constructed from two trivacant [B-α-GeW9O34]10 − Keggin moieties in a staggered fashion linked via a belt hexa-nickel cluster [Ni6(en)2(H2O)2]12 +. To our knowledge, 1 represents the first hexa-NiII substituted sandwich-type germanotungstate. 1 shows the occurrence of ferromagnetic interactions within nickel centers. The photocatalytic property of 1 has been investigated.An organic–inorganic hybrid hexa-nickel sandwiched germanotungstate has been hydrothermally synthesized and structurally characterized. The magnetic and photocatalytic properties have been investigated.Display Omitted► Sandwich-type Keggin germanotungstate. ► The hexa-nickel substituted sandwich-type germanotungstate. ► The ferromagnetic interactions within nickel centers. ► The photocatalytic property of germanotungstate.
Keywords: Polyoxometalate; Germanotungstate; Nickel; Sandwich-type structure;

Melamine-promoted crystal growth of calcium oxalate monohydrate from calcium nitrate and oxalic acid by Pounraj Thanasekaran; Chih-Ming Liu; Jhen-Fu Cho; Kuang-Lieh Lu (84-87).
The influence of melamine with different concentrations on the spontaneous batch crystallization of calcium oxalate monohydrate was investigated. The self-assembly of different sizes of calcium oxalate monohydrate crystals was achieved by layering a mixture of ethanol–water solutions of calcium nitrate and oxalic acid with different concentrations of melamine at room temperature. The presence of melamine accelerated the growth of large-sized calcium oxalate crystals but inhibited the total weight of the crystals. Precise EDX, IR and powder X-ray diffraction analyses of the product permitted its chemical composition to be determined. Such analyses lead to the finding that the reactions produced calcium oxalate monohydrate, that their average size increases from 1.5 × 10− 3 to 4.4 × 10− 3  cm3, while the total weight decreases from 3.6 to 1.5 mg with an increase of the amount of melamine. This finding is particularly significant for the renal and kidney failure due to the growth of large calcium oxalate monohydrate crystals in the presence of melamine.The influence of different concentrations of melamine on the spontaneous batch crystallization of different sizes and weights of calcium oxalate was found to be significant.Display Omitted► In this manuscript, we report on an investigation of the influence of different concentrations of melamine on the spontaneous batch crystallization of calcium oxalate. ► The self-assembly of different sizes of calcium oxalate crystals occurred when a mixture of ethanol-water solutions of calcium nitrate and oxalic acid was layered on different concentrations of melamine at room temperature. ► The presence of melamine accelerated the growth of large-sized calcium oxalate crystals but inhibited the total weight of the crystals. ► Precise EDX, IR and powder X-ray diffraction analyses of the product elucidate its chemical composition. ► This finding is significant, in particular, for renal and kidney failure due to the growth of large calcium oxalate crystals in the presence of melamine.
Keywords: Calcium oxalate; Crystal growth; Hydrogen-bonding; Melamine; Oxalic acid; Self-assembly;

An Exceptionally Stable Pb(II) Arene Compound by Jian-Kai Cheng; Xin Zhang; Ming-Jian Zhang; Yuan-Gen Yao (88-90).
A rare Pb(II) arene coordination polymer,[Pb(bimS)] (1; HbimSH = 2-mercaptobenzimidazole), has been solvothermally synthesized and characterized by single crystal X-ray diffraction, XRD, TGA, PL(photoluminescene), and UV–vis diffuse reflective spectra. The band structure and the densities of states of the title compound have been calculated to further understand the relation between the structure and optical property.An Exceptionally Stable Pb(II) Arene coordination polymer has been solvothermally synthesized and characterized by X-ray diffraction, XRD, TGA, PL(photoluminescene), and UV–vis diffuse reflective spectra. The band structure and the densities of states of the title compound have been calculated to further understand the relation between the structure and the optical property.Display Omitted► An exceptionally stable Pb(II) arene coordination polymer has been synthesized. Photoluminescence and UV-vis diffuse reflective spectra have been performed. ► The band structure and the densities of states have been calculated.
Keywords: Coordination polymer; Band structure; Densities of states; Optical property;

Construction of [EuZn(glycinate)(oxalate)2(H2O)2]n: An unusual heterometallic 3D 3d–4f coordination framework generated by in situ glycinate synthesis by Wen-Dong Song; Shi-Jie Li; Dong-Liang Miao; Li-Li Ji; Seik Weng Ng; Edward R.T. Tiekink; De-Yun Ma (91-94).
The 3D heterometallic 3d–4f coordination polymer, [EuZn(gly)(ox)2(H2O)2]n, 1, (gly = glycinate, ox = oxalate), was the product of the hydrothermal synthesis of glycinate from the reaction of tetrazole-1-acetic acid, sodium oxalate, zinc and europium salts in the presence of a trace quantity of nitric acid. Coordination polymer 1 exhibits an unusual 3D heterometallic coordination framework that is built up by heterometallic dinuclear EuZn secondary building units and mixed ox and gly linkers in a uninodal 6-connected vme {33.43.58.6} net. The solid-state photoluminescence and lifetime characteristics of 1 reveal intense red luminescence.Hydrothermal synthesis of the 3D heterometallic 3d–4f coordination polymer, [EuZn(gly)(ox)2(H2O)2]n, 1, (gly = glycinate, ox = oxalate), involving the in situ generation of glycinate, leads to a material that displays intense red luminescence properties.Display Omitted► A new 3-D heterometallic 3d–4f polymer has been synthesized. ► Heterometallic dinuclear EuZn secondary building units are found in an uninodal 6-connected vme {33.43.58.6} net. ► In situ hydrothermal glycinate synthesis. ► Intense red luminescence in the solid-state.
Keywords: Hydrothermal synthesis; Heterometallic complex; In situ glycinate synthesis; Luminescence; Crystal structure;

A novel α-Po interpenetrating network with pseudo-double-wall pcu lattices based on the homoleptic nickel(II) node by Peng-Cheng Wang; Fan-Li Meng; Chao Liu; Kang-Yu Zou; Zuo-Xi Li (95-98).
A novel coordination polymer, {[Ni(bib)3](ClO4)2} (1), was synthesized by the reaction of Ni(ClO4)2·6H2O with a linear rigid ligand 1,4-bis(imidazol-1-yl)benzene (bib). In this complex, the homoleptic octahedral nickel(II) node is connected by the rod-like spacer bib into an α-Po framework with larger pcu lattices, which are seemingly surrounded by double walls. The void space provided by the square-shaped channel is filled with another equivalent framework, i.e. complex 1 representing a unique interpenetrating α-Po topology network. Furthermore, magnetic study shows that there exists very weak antiferromagnetic exchange coupling in the complex.A novel coordination polymer has been constructed by the assembly of homoleptic NiII center with a rod-like spacer 1,4-bis(imidazol-1-yl)benzene, which features a unique interpenetrating α-Po network with pseudo-double-wall lattices. The very weak antiferromagnetic property is also found in this complex.Display Omitted► A novel and rare homolepti framework constructed from a rod-like spacer bib. ► The title complex displays a unique interpenetrating a-Po network. ► The interpenetrating network presents a pseudo-double-wall structure.
Keywords: Coordination polymer; Bis(imidazole) rigid ligand; Homoleptic nickel(II) node; α-Po interpenetrating network; Magnetic property;

Three new complexes, namely, [M(Pim)(L)] (M = Co (1), Cd (2), Pim = Pimelic acid, L = 1,4-bis(1-imidazolyl)-benzene), [Zn(Pim)(L)]·H2O (3), have been synthesized hydrothermally from the self-assembly of the transtion metal ions (M2 +) with flexible aliphatic dicarboxylate ligand (Pim) and the rigid bis(imidazole) ligand(L). Both complexes 1 and 2 consist of left- and right-handed single-helical chains and present a two-dimensional (2D) layer with 36-hxl topology. Complex 3 displays a 2D structure constructed by right-handed single-helical chains and left-handed double-helical chains with intercrossed arrangement. Furthermore, thermogravimetric analyses for 13 and the photoluminescent properties of 2 and 3 have also been studied.Syntheses and characterizations of three novel 2D complexes based on pimelic acid and rigid bis(imidazole) ligand are discribed. Complexes 1 and 2 display as 36-hxl nets with left- and right-handed single-helical chains. Complex 3 is constructed by right-handed single-helical chains and left-handed double-helical chains with intercrossed arrangement. Their thermal and photoluminescent properties have also been investigated.Display Omitted► Three 2D complexes with helical chains have been synthesized and characterized. ► 1 and 2 consist of left- and right-handed helical chains and display 36-hxl nets. ► 3 consists of single-helical and double-helical chains with intercrossed arrangement.
Keywords: Coordination complexes; helical chains; Pimelic acid; Bis(imidazole) ligand; Photoluminescent property;

A novel coordination polymer [La(L)(H2O)]n (1) has been prepared by hydrothermal reaction of 5-hydroxyisophthalic acid (H3 L) with La(NO3)3·6H2O, which exhibits an unusual three-dimensional (3D) (6,6)-connected nia net with Point (Schläfli) symbol of (412.63)(49.66). Meanwhile, a two-dimensional (2D) (3,6)-connected (32.4)(34.43.52.65.7) coordination network {[Ho2(HL)3(H2O)2]·H2O}n (S1) was also obtained with partially deprotonated HL 2– ligand. Comparison of the structural differences between 1 and S1 suggests that the different metal sources play an important role in the construction of such coordination networks.Two coordination polymers, [La(L)(H2O)]n (1) and {[Ho2(HL)3(H2O)2]·H2O}n (S1) (H3 L  = 5-hydroxyisophthalic acid), have been prepared. Complex 1 exhibits the nia topological net with Point (Schläfli) symbol of (412.63)(49.66), whereas complex S1 has a 2D (3,6)-connected (32.4)(34.43.52.65.7) topology. Remarkably, complex 1 is the first lanthanide network with the hydroxyl group of 5-hydroxyisophthalic acid coordinating to the metal atoms.Display Omitted► A unique 3D LaIII nia network with (412.63)(49.66) topology. ► Structure modulation driven by different metal sources. ► The hydroxyl group of 5-hydroxyisophthalic acid coordinating with LaIII
Keywords: Lanthanide complexes; Crystal structures; Topology; Properties;

Characterization of a well-resolved acyclic methanol(water)5 heterohexamer in the solid state by Geng-Geng Luo; Dong-Xu Li; Dong-Liang Wu; Li Liu; Qing-Hua Zhao; Cheng Peng; Zi-Jing Xiao; Jing-Cao Dai (108-112).
A novel (CH3OH)(H2O)5 binary cluster is trapped in a photoluminescent silver(I) coordination polymeric host, [Ag2(bpp)2(H2O)(ssa)·4H2O·CH3OH]n (1, bpp = 1,3-bis(4-pyridyl)propane, H2ssa = 5-sulfosalicylic acid). The heterohexamer can be viewed as either a D 5 water pentamer with a dangling methanol molecule or a combination of D 4 tetrameric water and methanol–water heterodimer. This well-resolved heterohexamer may behave as a useful model helping us to further understand phase behavior of binary methanol–water system. The luminescent behavior of 1 was also discussed.A novel (CH3OH)(H2O)5 binary cluster which is trapped in a photoluminescent silver(I) coordination polymeric host, [Ag2(bpp)2(H2O)(ssa)·4H2O·CH3OH]n (1, bpp = 1,3-bis(4-pyridyl)propane, H2ssa = 5-sulfosalicylic acid) has been determined by single-crystal X-ray analysis.Display Omitted► A novel silver(I) complex 1 has been synthesized and characterized by single-crystal X-ray analysis. ► A rare (CH3OH)(H2O)5 binary cluster was observed in 1. ► The heterohexamer can be viewed as a combination of a D 5 water pentamer and a methanol molecule. ► The luminescent behavior of 1 was also discussed.
Keywords: Silver(I); 1,3-bis(4-pyridyl)propane; 5-sulfosalicylic acid; Water pentamer; Methanol–water binary cluster; DFT calculation;

Two unusual cyclometalated dimeric Ir(III) complexes: Synthesis, crystal structure and phosphorescent properties by Bihai Tong; Jiayan Qiang; Qunbo Mei; Hengshan Wang; Qianfeng Zhang (113-115).
Two cyclometalated dimeric Ir(III) complexes, [{Ir(μ-Cl)(μ-ppa)(dmppa)}2] (dimer 1) and (dmppa)Ir(μ-Cl)(μ-ppa)Ir(ppa) (dimer 2) (dmppa = 1-(2,6-dimethylphenoxy)-4-phenylphthalazine, ppa = 1-hydroxyl-4-phenylphthalazine), containing the bridging phthalazine ligands and bridging chlorides have been synthesized and fully characterized. Dimer 1 can form a noncovalently linked crystalline porous frameworks. The emission wavelength of dimer 1 in CH2Cl2 solution was 596 nm and the further hydrolysis of phenolic groups red shift the emission of dimer 2 to 634 nm. Two dimers have relatively high quantum efficiency, i.e., ca. 0.21 for dimer 1 and 0.3 for dimer 2 in CH2Cl2 solution.Two cyclometalated dimeric Ir(III) complexes, dimer 1 and dimer 2 containing the bridging phthalazine ligands and bridging chlorides have been synthesized and fully characterized. Dimer 1 can form a noncovalently linked crystalline porous frameworks. The emission wavelength of dimer 1 in CH2Cl2 solution was 596 nm and the further hydrolysis of phenolic groups red shift the emission of dimer 2 to 634 nm.Display Omitted► Two cyclometalated dimeric Ir(III) complexes containing bridging phthalazines and chlorides were reported. ► A noncovalently linked crystalline porous frameworks was found. ► The influence of the phenolic groups hydrolysis to the emission wavelength of dimer was discussed. ► New dimers have relatively high quantum efficiency.
Keywords: Dimeric iridium complex; Crystal structure; Photoluminescence;

Two new copper(I) complexes [Cu(L 1 )2]PF6 (L 1  = 4-diphenylphosphino-1,5-naphthyridine, 1) and [Cu(L 2 )2]PF6 (L 2  = 4-diphenylphosphino-8-methyl-1,5-naphthyridine, 2), have been prepared and characterized. In each of them, the coordinate geometry of Cu atom is a distorted square planar configuration with bond distances and angles in the normal range. Moreover, compound 2 features one-dimensional zigzag chains which are cross-linked by the metal complex cations and PF6 anions through hydrogen bonding interactions. The HOMO–LUMO energy gaps of 12 estimated by the cyclic voltammetry (CV) show values in the order of 1  >  2. Both 1 and 2 show low-energy bands ranging from 360 to 430 nm and available florescence in the solid state at room temperature with λmax  = 532–541 nm. The UV–vis absorption spectra of 12 show obvious red-shifts compared with those of the corresponding quinoline containing Cu(I) complexes [Cu(QN)2]PF6 (QN = 8-diphenylphosphino quinoline), exhibiting the HOMO–LUMO energy gaps of 12 should be narrower than that of [Cu(QN)2]PF6.Complex 1(RT) crystallizes with two molecules per asymmetric unit. Compound 2 features one-dimensional zigzag chains through hydrogen bonding interactions. Both 1 and 2 show low-energy bands ranging from 360 to 430 nm and available florescence in the solid state at room temperature with λmax = 532–541 nm.Display Omitted► 4-Diphenylphosphino-1,5-naphthyridine ligands are first introduced into the system of Cu(I) complexes. ► X-ray determinations of complexes 12 reveal that the central copper(I) ions assume highly distorted tetrahedral geometry. ► Electrochemistry and photophysical properties of the complexes are investigated. ► These new Cu(I) complexes show narrower HOMO–LUMO energy gaps compared to analogous quinoline containing complexes.
Keywords: Copper(I) complexes; 1,5-Naphthyridine; HOMO–LUMO energy gaps; Red-shifts; Florescence;

A novel 4-aminoantipyrine derived Schiff base and its four mixed ligand complexes have been synthesized and characterized. The binding properties of metal complexes with DNA have been investigated by electronic absorption spectra and viscosity measurements showing that the complexes have the ability of interaction with DNA by intercalative mode. The effect of the metal complexes on DNA was carried out by pUC19 DNA agarose gel electrophoresis at 50 V for 2 h. The damage effect of the added ascorbic acid into the medium is dependent on the free radicals produced from oxidation of ascorbic acid by molecular oxygen and this damage is considered to be reduced by the metal complexes.The synthesized mixed ligand metal complexes are effective intercalators. They contribute to the development of novel drugs which specifically target DNA, essential for understanding the action mechanism of few DNA-targeted drugs and toxic agents as well as the origin of few diseases like gene mutation.Display Omitted► These complexes display good DNA binding and chemical nuclease activity. ► The scope of this work is to develop the novel antitumor drugs targeted to DNA. ► 4-aminoantipyrine based metal complexes are found to be good DNA binding agents.
Keywords: Mixed ligand metal complexes; Schiff base; DNA binding; DNA damage;

The preparation as well as spectroscopic and structural characterization of some oxovanadium(IV) and dioxovanadium(V) complexes containing deprotonated selenosemicarbazone ligands is reported.The preparation as well as spectroscopic and structural characterization of two oxovanadium(IV) and dioxovanadium(V) complexes containing a deprotonated selenosemicarbazone ligands is reported. The monoanionic ligand coordinates to the vanadium centre in a tridendate fashion through two nitrogen atoms and a selenium atom. The green paramagnetic oxovanadium(IV) compound is oxidised to the diamagnetic yellow dioxovanadium(V) complex in solution.Display Omitted► We report the preparation and spectral characterisation of the first vanadium complexes with selenosemicarbazone ligands. ► The structures of an oxovanadium(IV) and a dioxovanadium(V) complex are presented. ► Some preliminary reactivity studies have been carried out with the vanadium(IV) compound.
Keywords: Selenosemicarbazone; Vanadium; X-ray structure; Peroxido complexes;

Copper(I)-promoted halogen exchange in the iron(II) dichloroclathrochelate by Yan Z. Voloshin; Oleg A. Varzatskii; Sergey V. Shul'ga; Irina N. Denisenko; Anna V. Vologzhanina; Yurii N. Bubnov (128-131).
The halogen exchange reaction of the macrobicyclic iron(II) complex FeBd2(Cl2Gm)(BF)2 (where Bd2– and Cl2Gm2– are α-benzyldioxime and dichloroglyoxime dianions, respectively) with two-fold excess of CuI and stoichiometric amounts of NaI in NMP gave the mixture of initial compound with diiodo- and iodochloroclathrochelates as well as the small amounts of the cage by-products of side hydrodehalogenation and homo-coupling reactions of this precursor. The chromatographically isolated complex FeBd2(IGmCl)(BF)2 has been characterized using elemental analysis, MALDI-TOF mass spectrometry, IR, UV–vis, 1H and 13C{1H} NMR spectroscopies, and X-ray diffraction crystallography. This clathrochelate possess a geometry intermediate between that of a trigonal prism and a trigonal antiprism (the distortion angle φ  = 23.6°). The Fe–N distances vary in a narrow range (1.91–1.92 Å), the height h of the FeN 6 -coordination polyhedron and the averaged bite angle α are equal to 2.34 Å and 39.2°, respectively. The reaction studied occurs only in the case of the vic-dihalogenosubstituted macrobicycles with CuI as both the catalyst and the reagent, and with iodide anions coordinated to the copper(I) ions. The proposed mechanism of this reaction is similar to that for copper-catalyzed Finkelstein-type reactions of aryl halides and the intermediate anion-radical species are effectively generated with CuI–N-methylpyrrolidone complex.The reaction of the iron(II) dichloroclathrochelate with CuI and NaI in NMP gave the mixture of the homo- and heterodihalogenomacrobicycles. The reaction with Cu(I)–NMP system occurs only in the case of the vic-dihalogenosubstituted complexes. This halogen exchange reaction is useful for other electron-deficient metal complexes and organic compounds.Display Omitted► The halogen exchange reactions of the iron(II) dihalogenoclathrochelates with copper(I) iodide–NMP system was studied. ► Reaction of the iron(II) dichloroclathrochelate with this system gave the mixture of homo- and heterodihalogenomacrobicycles. ► The reaction occurs with CuI as both the catalyst and the reagent in the case of the vic-dihalogenosubstituted macrobicycles. ► Complex Na[CuI2(NMP)n] with iodide anions, which are coordinated to the copper(I) ion, was used as a reagent. ► This halogen exchange reaction is useful for other electron-deficient metal complexes and organic compounds.
Keywords: Macrocyclic compounds; Clathrochelates; Iron complexes; Copper-promoted reactions; Ligand reactivity;

Spectroscopy, thermal analysis and crystal structure of a novel diammonium bis[hexaaquazinc(II)] decavanadate tetrahydrate by Anurak Udomvech; Prachit Kongrat; Chaveng Pakawatchai; Hirihattaya Phetmung (132-136).
A synthesis between NH4VO3 and Zn(CH3COO)2·2H2O in aqueous solution resulted in a novel decavanadate compound. Its single crystal X-ray diffraction analysis revealed the decavanadate cage-like structure [V10O28]6− form the discrete anionic cluster which associated to binary cationic groups, (NH4)+ and [Zn(H2O)6]2+, into the neutral (NH4)2[Zn(H2O)6]2V10O28  ⋅ 4H2O compound. The principal feature of the crystal supramolecularity is non-covalent weak interactions from two cations and decavanadates forming the 3D framework. The FT-IR spectra illustrate the strong bands of V=O. Thermogravimetric studies reveal the complete removal of all water molecules ammonium cations and vanadate in multiple steps ranging from 30 to 400 °C.The novel compound has been successful synthesized and characterized. Its crystal structure revealed a polyoxovanadate cage-like structure [V10O28]6− form the discrete anionic cluster which associated to binary cationic groups, (NH4)+ and [Zn(H2O)6]2+, into the neutral (NH4)2[Zn(H2O)6]2V10O28  ⋅ 4H2O compound. The non-covalent weak interactions occurred via N–H···O and O–H···O hydrogen bondings make the supramolecular assembly network.Display Omitted► A simple route to synthesis with a high yield and mild condition. ► IR and TGA studies clearly confirmed its component of novel polyoxovanadate. ► Polyoxovanadate is a 3D network based on decavanadate and binary cations
Keywords: Decavanadate; Polyoxovanadate; Binary cations; Cage-like structure; Isostructures;

A novel 3D (3,5)-connected metal–organic framework based on a flexible hexacarboxylate by Ying-Ying Liu; Ting-Ting Zhang; Jian-Fang Ma; Jin Yang; Shu-Yan Song (137-141).
A novel three-dimensional (3D) metal-organic framework, [Cd2(HL)(H2O)2]·H3O·0.25(imi) 1, (H6L = 5,5′,5″-(2,4,6-trimethylbenzene-1,3,5-triyl)trismethylene-trisoxy-triisophthalic acid and imi = imidazole) has been prepared under hydrothermal condition. Compound 1 possesses a 3D (3,5)-connected framework with (52·8)(5·6·8)(6·82)(52·6·85·9·10) topology. The thermogravimetric and luminescent properties have also been studied for the compound.A novel three-dimensional (3,5)-connected metal-organic framework, [Cd2(HL)(H2O)2]·H3O·0.25(imi) 1, has been hydrothermally synthesized, where the thermogravimetric and luminescent properties have also been discussed for the compound.Display Omitted► The 3D net contains one-dimensional rectangular-shaped channels. ► The structure displays a rare (3,5)-connected (52·8)(5·6·8)(6·82)(52·6·85·9·10) topology. ► The emission of 1 may be attributed to the intraligand charge transfer of HL anion.
Keywords: Cadmium; Coordination polymers; Hexacarboxylates; Luminescence;

Two new coordination compounds, [Mn(HL)(H2O)2] n (1) and {[Mn12(L)8(H2O)30]∙10H2O} n (2) were successfully synthesized by using a hydrothermal technique under different pH values and characterized by single-crystal X-ray diffraction. 1 formed at lower pH value (6.0) exhibits 2D lamellar framework which is further connected by hydrogen-bond interactions to construct a 3D supramolecular architecture. Reaction at pH = 7.5 leads to a 2D layered structure of 2, which are formed through the interconnection of the dodecanuclear units and the completely depronated ligands. It is comprehensible that the pH value plays a crucial role in the formation of the resulting structures. Variable temperature magnetic studies down to 2 K reveal antiferromagnetic interactions in complexes 1 and 2.Two MnII coordination polymers with totally different structures are constructed by pH-controlled assemblies.Display Omitted► Two MnII complexes were successfully synthesized by altering pH conditions. ► The pH value significantly affects the formation of the resulting structures. ► Furthermore, their magnetic properties and thermal stability were investigated.
Keywords: Crystal engineering; Manganese; pH value influence; Magnetic properties;

In this paper, we report on a facile and environmentally friendly large-scale synthesis of metal–organic framework (MOF) nanowires by using an ultrasonic method without the introduction of any seeds, polymers, or surfactants. Highly luminescent nanowires of a one-dimensional terbium benzenetricarboxylate MOF, [Tb(1,3,5-btc)(H2O)6]n (1,3,5-btc = benzene-1,3,5-tricarboxylate), with an average diameter of 50 nm and lengths of up to a few micrometers can be easily obtained in a relatively high yield under ultrasound irradiation at 70 °C and under atmospheric pressure. The structure and morphology of the as-synthesized MOF nanowires were characterized by powder X-ray diffractometry (PXRD) and field emmision scanning electron microscopy (FE-SEM), respectively. The [Tb(1,3,5-btc)(H2O)6]n nanowires obtained show strong luminescence emission at 548 and 492 nm, and exhibit high selectivity for sensing of aromatic amines, such as aniline and p-phenylenediamine, in comparison with alkylamines (e.g. methylamine, ethylamine, n-propylamine, n-butylamine and triethylamine). Such a significantly selective luminescence quenching effect of [Tb(1,3,5-btc)(H2O)6]n nanowires for aromatic amines makes the nanostructured Tb-MOF-based sensing materials potential for sensing of aromatic amines in a mixture solution of organoamines.Highly luminescent nanowires of a lanthanide metal–organic framework (MOF), [Tb(1,3,5-btc)(H2O)6]n, have been successfully fabricated by an ultrasonic method, and the as-prepared MOF nanowires exhibit significantly high selectivity for sensing of aromatic amines.Display Omitted► Highly luminescent nanowires of a lanthanide metal–organic framework (MOF). ► Rapid synthesis of MOF nanocrystals under ultrasonic irradiation. ► High sensitivity of the [Tb(btc)(H2O)6]n MOF nanowires to aromatic amines.
Keywords: Metal–organic framework; Nanowires; Ultrasonic synthesis; Sensing materials; Luminescence quenching;

Two new sandwich-type tungstobismuthates constructed from trivacant Keggin units, estertin and transition metals by Zan-Jiao Wang; Lan-Cui Zhang; Zai-Ming Zhu; Wei-Lin Chen; Wan-Sheng You; En-Bo Wang (151-154).
Two new sandwich-type tungstobismuthates containing carboxyethyltin groups and transition metals, Na8K2[{Co(H2O)3}2{Sn(CH2)2COO}2·(B-β-BiW9O33)2]·25H2O (1) and K10[{Mn(H2O)3}2{Sn(CH2)2COO}2·(B-β-BiW9O33)2]·30H2O (2) have been synthesized in the aqueous solutions and characterized by IR, TG, NMR and XRD. Single crystal X-ray diffraction analysis reveals that two 3d-transition metal (TM) cations and two organometallic (OM) groups in the central belt of the two complexes are all sandwiched by two B-β-[BiW9O33]9− units. The two compounds represent the first transition metal and carboxyethyltin-decorated polyoxometalate complexes. Structural analyses reveal that the reaction processes involving the α  →  β isomerization of [BiW9O33]9− unit and the hydrolysis of ester group. Both compounds have high thermal stabilities.Two new sandwich-type tungstobismuthates containing carboxyethyltin groups and transition metals are obtained, displaying high thermal stabilities.Display Omitted► The organotin groups are firstly decorated on the B-β-[BiW9O33]9− units. ► The two compounds represent the first transition metal and carboxyethyltin-decorated polyoxometalate complexes. ► Compounds 1 and 2 have high thermal stabilities.
Keywords: Sandwich-type tungstobismuthate; Trivacant Keggin anion; Estertin; Transition metal;

Self-assembly of high-dimensional architecture from Strandberg-type polyoxometalate clusters and silver ions by Chun-Xia Zhang; Ya-Guang Chen; Qun Tang; Zhi-Chao Zhang; Dan-Dan Liu; Hua-Xin Meng (155-158).
A new three-dimensional (3D) compound [Ag12(OH)2(H2O)4KNa(P2Mo5O23)2] (1), was synthesized by the liquid diffusion method and characterized by single crystal X-ray diffraction analysis, elemental analysis, IR spectroscopy and thermal gravimetric analysis. In 1, two crystallographically independent P2Mo5 clusters are surrounded by thirty-seven Ag+ ions, three K+ ions and three Na+ ions, representing the highest connected number of the Strandberg-type POMs to date. There are twelve crystallographically unique silver cations, which have different coordination geometries: distorted triangular prism, distorted octahedron, distorted square-pyramid and distorted trigonal bipyramid. All the Strandberg-type units are interlinked by Ag (I) forming a 3D arrangement through O-Ag-O bridging bonds. The luminescent property of the compound 1 is tested in the solid state.A new compound [Ag12(OH)2(H2O)4KNa(P2Mo5O23)2] (1), was synthesized by the liquid diffusion method and conventionally characterized, in which the inorganic layers formed by the coordination of diphosphopentamolybdate anions to sliver ions are linked by Ag6 clusters forming a unique 3D framework.Display Omitted► The compound represents the first example of silver compound based on P2Mo5 cluster. ► A unique 3D framework is formed by P2Mo5-Ag layers and Ag6 clusters. ► Two P2Mo5 clusters are surrounded by thirty-seven Ag+ ions. ► Twelve crystallographically unique silver ions are in different geometries.
Keywords: Strandberg-type polyoxometalate; Silver; Diphosphopentamolybdate; Liquid diffusion method; Crystal structure;

Isosymmetric temperature-triggered structural phase transition of dabcodiium chlorochromate chloride by Heng-Yun Ye; Hong- Ling Cai; Jia-Zeng Ge; Ren-Gen Xiong (159-162).
Dabcodiium chlorochromate chloride was synthesized and separated as crystals. DSC measurement shows that this compound undergoes a reversible phase transition at about 185 K with a heat hysteresis of 5 K. Step-like dielectric anomaly observed at 187 K further confirms the phase transition. The crystal structures determined at 173 and 296 K are all monoclinic in P21/m, showing that the phase transition is isosymmetric. The transition is realized by tripling the a-axis without changing the b, c-axes, and β angle. A 60° rotation of one of every three CrO3 groups around the Cr-O bond is probably the driving force of the transition. Hydrogen bonding effect on the transition was shown to be negligible.The DSC measurement, dielectric measurement and variable-temperature single crystal X-ray diffraction analysis reveal that dabcodiium chlorochromate chloride undergoes reversible phase transitions at about 185 K. The relationship between the two cells is 3a, b, c (RT) approximates a, b, c (LT). Structural analysis shows that a 60° rotation of one of every three CrO3 groups may be the driving force of the transition, whereas hydrogen bonding effect is negligible.Display Omitted► Dabcodiium chlorochromate chloride undergoes an isosymmetric temperature-triggered structural phase transition. ► The relationship between the two cells is 3a, b, c (RT) approximates a, b, c (LT). ► The transition mechanism is related to a 60° rotation of one of every three CrO3 groups around the Cr–Cl bond. ► The transition results in thermal and dielectric anomaly.
Keywords: Structural phase transition; Order parameter; Hydrogen bonding effect; Dielectric response;

A series of LMOFs, consisting of three groups of isostructural compounds, [Ln(3-H-5-phenoxonicotinato)(ox)(H2O)2]n 1 (Ln = La(1a), Pr(1b), Nd(1c), 5-Hydroxynicotinic acid = C6H5NO3, ox = C2O4 2 −), {[Ln(3-H-5-hydroxynicotinato)(ox)1.5(H2O)]⋅H2O}n 2 (Ln = Sm(2a), Gd(2b), Tb(2c), and {[Ln(3-H-5-phenoxonicotinato)(ox)(H2O)]⋅H2O}n 3 (Ln = Dy(3a), Er(3b), have been hydrothermally synthesized and structurally determined by X-ray diffraction analyses. Compounds in group 1 are constructed by mixed μ 3-3-H-5-phenoxonicotinato and oxalate bridging ligands and Ln3 + ions, exhibiting a 3D covalent network with empty 1D microchannels, featuring a 3,5-connected topology symbol of {42⋅ 65⋅ 83}⋅{42⋅ 6}. Compounds in group 2 present a brick-well-liked 2D network generated by both metal ions and oxalate groups at a side-by-side way. Compounds in group 3 are isotopological to those in group 1, accompanying 1D microchannels being occupied by coordinated water molecules. Antiferromagnetic interactions between praseodymium metal centers are observed from the magnetic susceptibility of compound 1b. In addition, luminescence measurements indicate that the terbium complex 2c is a strong green luminescence emitter.Eight new lanthanides metal-organic frameworks (LMOFs) [Ln(3-H-5-phenoxonicotinato)(ox)(H2O)2]n 1 (Ln = La(1a), Pr(1b), Nd(1c)), {[Ln(3-H-5-hydroxynicotinato)(ox)1.5(H2O)]⋅H2O}n 2 (Ln = Sm(2a), Gd(2b), Tb(2c), and {[Ln(3-H-5-phenoxonicotinato)(ox)(H2O)]⋅H2O}n 3 (Ln = Dy(3a), Er(3b), have been hydrothermally synthesized and structurally determined. The study on magnetic property of complex 1b reveals antiferromagnetic interactions existing between neighboring praseodymium(III) ions and the study of luminescent property about compound 2c shows that the terbium compound is a green luminance emitter.Display Omitted► Reaction of Ln3 + ions with 5-Hydroxy-nicotinic acid and oxalate forms eight LMOFs. ► The 2D LMOFs (Ln = Sm/Gd/Tb) show a brick-well-liked covalent network. ► The 3D LMOFs (Ln = La/Pr/Nd/Dy/Er) hold a 3,5-connected {42⋅ 65⋅ 83}⋅{42⋅ 6} topology. ► The praseodymium complex exhibits antiferromagnetic interactions. ► The terbium compound is a strong green luminance emitter.
Keywords: Lanthanides metal-organic frameworks; 5-Hydroxynicotinic acid; Magnetic property; Luminescent property; Crystal structures;

A new cationic copper–iodine based metal–organic framework compound, [Cu7I4L3(H2O)]n (1) (L = 5-(3-pyridyl)tetrazole), has been synthesized by solvothermal method. X-ray analysis shows that compound 1 is a 3-D metal–organic framework constructed by the L ligands linking new discrete (Cu7I4)3 + cationic clusters, which has an uncommon (3, 9)-connected gfy topological network including 1D hexagonal nano-channels.Presented here is a new 3D metal-organic framework [Cu7I4L3(H2O)]n (1) (L = 5-(3-pyridyl)tetrazole), has been synthesized by solvothermal method. Structural analysis shows that compound 1 is an interesting (Cu7I4)3 + cluster-based metal–organic framework (MOF) with uncommon (3, 9)-connected gfy topology.Display Omitted► Unprecedented cationic [Cu7I4]3 + cluster was trapped by solvothermal synthesis of an anionic-tetrazolate-based metal organic framework. ► The metal organic framework with unprecedented (3,9)-connected gfy topology. ► Representing the first Cu–I cluster based MOF with the gfy topology and 1D hexagonal nano-channels.
Keywords: Cu–I cluster; Tetrazole; Topology; MOFs;

Two coordination polymers, [Zn(EDDT)0.5(H2O)2] (1) and [Zn(EDDT)0.5(BPE)]⋅xG (2) (EDDT = 2,2’-(ethyne-1,2-diyl)diterephthalate, BPE = 1,2-bi(4-pyridyl)ethane, G = guest molecule), were solvothermally synthesized from the rigid planar linker of EDDT and the coligand of BPE, respectively, in which complex 1 displays 2D [Zn(EDDT)0.5] coordination layer, and the resulting 3D supramolecular network is formed via interlayer H-bonding interactions, whereas complex 2 exhibits an intriguing micropourous framework via the coordination of auxiliary ligand BPE. Interestingly, both of them show enhanced strong blue luminescence.Two novel coordination polymers, 2D layer motif of [Zn(EDDT)0.5  ∙ 2H2O] (1) and 3D microporous network of [Zn(EDDT)0.5∙(BPE)]⋅xG (2), built from the rigid planar ligand 2,2'-(ethyne-1,2-diyl)diterephthalate (EDDT) and the pillaring auxiliary ligand 1, 2-bi(4-pyridyl)ethane (BPE), exhibit enhanced strong solid-state luminescence.Display Omitted► Zinc coordination polymers built from rigid planar tetracarboxylate ligand of 2, 2'-(ethyne-1, 2-diyl)diterephthalate (EDDT). ► 2D layered or 3D micropourous supramolecular network. ► Strong blue emission in the solid state at room temperature.
Keywords: Coordination polymers; Luminescence properties; Solvothermal synthesis; 2,2’-(Ethyne-1,2-diyl)diterephthalate; Zn(II) complex;

For the purpose of investigating the effect of sulfur ligands on the metal complex electronic states, a soft scorpionate ligand, which bears three sulfur coordination sites on a molecule, was used to afford a novel high-spin cobalt(II) complex, [CoII(Tbz)2] (Tbz  = hydrotris(2-mercaptobenzothiazolyl)borate), having an octahedral [CoIIS6] core. Based on the electronic spectrum of the complex consisting of two d-d bands, the ligand-field splitting and the Racah parameter were estimated as Δ 0/hc  = 8000 cm− 1 and B/hc  = 560 cm− 1, respectively. The latter proved remarkable nephelauxetic effect arising from delocalization of d-electrons over the ligands. These parameters were successfully utilized in the simulation of the magnetic susceptibility.A novel cobalt(II) soft-scorpionate complex [CoII(Tbz)2] having an octahedral [CoIIS6] core was synthesized. The diffuse reflectance spectrum demonstrated that the Tbz ligand gives a small ligand-field splitting and a strong nephelauxetic effect. Remarkable delocalization of d-electron onto the ligand moieties was also suggested from the simulation of the magnetic behavior.Display Omitted► A novel cobalt(II) soft-scorpionate complex [CoII(Tbz)2] was synthesized. ► The electronic spectrum of [CoII(Tbz)2] proved intense nephelauxetic effect. ► Magnetic susceptibility also suggests remarkable d-electron delocalization.
Keywords: CoII complex; Soft scorpionate; Nephelauxetic effect; Magnetic property; Ligand-field theory;

The hydrothermal reaction of CdCl2·2.5H2O with 3,5-bis-oxyacetate-benzoic acid (H3BOABA) and 4,4′-bis(1-imidazolyl)biphenyl (L) generates a new three-dimensional (3D) coordination polymer, {[Cd2(BOABA)(L)(μ 3-OH)]2·3H2O}n (1). In 1, the Cd(II) centers are connected by carboxylate and μ 3-OH bridges into Cd-O-C rod-like secondary building units (SBUs) which are further linked by BOABA3 − and L ligands into the 3D framework. Two types of irregular rhombic channels occupied by free water molecules were observed in the framework. And the topology analysis suggests an unusual (4,8)-connected net for 1. Furthermore, the thermal and photoluminescent properties of 1 have also been studied.This paper described the synthesis and characterizations of one novel complex based on 3,5-bis-oxyacetate-benzoic acid and rigid bis(imidazole) ligand. Complex 1 consists of Cd-O-C rod-like secondary building units (SBUs) and displays a three-dimensional (4,8)-connected net. The thermal and photoluminescent properties of 1 have also been investigated.Display Omitted► One new 3D complex based on mixed O- and N-donor ligands was described. ► Complex 1 consists of Cd-O-C rod-like SBUs and displays a (4,8)-connected net. ► The thermal and photoluminescent properties of 1 have also been investigated.
Keywords: Coordination polymer; Rod-like SBUs; (4,8)-connected net; Photoluminescence;