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1, 4, 5, 8‐naphthalene diimide (NDI)‐based MOFs, due to their tunable structures and properties, have shown promising applications in photochromism, photocatalysis, electrocatalysis, photothermal therapy, etc. Herein, using an L‐alanine modified NDI ligand, i.e. N, N′‐bis(L‐alanine)naphthalenediimide (AlaNDI), a novel Cd‐NDI Cd (AlaNDI)(H2O)]·DMF·H2O (complex 1) was constructed under solvothermal conditions, which has an obvious different structure with the previously reported ones. Structural analysis shows that the packing structure of complex 1 consists of two adjacent Cd atoms sharing two AlaNDI ligands, forming a dimetallic building block [Cd2O8]. Each building block connects a total of four AlaNDI ligands, where two Cd atoms are bridged by two ligands. The building blocks are interconnected by ligands to form a two‐dimensional layered structure. Based on the features of the NDI skeleton, it was found that complex 1 possesses multiple stimulus responses involving sensitivity to light: a reversible photochromism property and good photocatalytic degradation activity against various dyes, especially against cationic dyes crystal violet (CV), methyl violet (MV), and Janus green B (JGB). In addition, the stimulus‐response mechanism was investigated by control experiments. It is revealed that the photocatalytic active species may be related to h+ and •OH. [ABSTRACT FROM AUTHOR]

Thorium‐based metal–organic frameworks (MOFs) are unique, which are substantially less reported compared to the MOFs based on transition metal and rare earth elements. Here, a thorium‐MOF (Th‐TCBPE) based on 4',4'',4''',4''''‐(ethene‐1,1,2,2‐tetrayl)tetrakis([1,1'‐biphenyl]‐4‐carboxylic acid) (H4TCBPE) and thorium nitrate is synthesized first. Th‐TCBPE is an interpenetrated 2D network, where Th (IV) is ten‐coordinated with a bicapped dodecahedron coordination geometry. Further studies about the structure by time‐resolved emission spectra (TRES) analysis are also discussed. What's more, Th‐TCBPE has excellent thermal stability and good tunable AIE property on concentration in THF. The photophysical properties of Th‐TCBPE in different solvents, different concentrations in THF, and different ratios of THF/H2O are studied. The ability of Th‐TCBPE to detect nitro aromatic compounds is also investigated. It is also believed that this work can provide theoretical guidance and inspiration for the development of Th‐MOF and MOF with AIEgens in the future. [ABSTRACT FROM AUTHOR]

The complex [Cd(PDNDI)]·DMF (Cd‐PDNDI) (H2PDNDI = N‐(4‐pyridine)‐4,5‐dicarboxy‐1,8‐naphthalene dicarboxyimide) was synthesized by the reaction of N,N′‐di(4‐pyridyl)‐1,4,5,8‐naphthalene diimide (DPNDI) and Cd(NO3)2·4H2O. It was characterized by elemental analysis, infrared spectroscopy, ultraviolet–visible (UV‐vis) spectroscopy, powder X‐ray diffraction (PXRD), single crystal X‐ray diffraction, and thermogravimetric analysis. Structural analysis shows that the Cd‐PDNDI has a self‐assembled 3D network structure with the rtl type topology. It is worth mentioning that the composition of the ligand is different from the initial raw material used in this molecular structure. This may be because the ligand undergoes an in situ hydrolysis reaction in the reaction system and becomes an NDI carboxylic acid derivative, which continues to join coordination reaction with the metal ion. In addition, the Cd‐PDNDI has an excellent photocatalytic effect on malachite green (MG) among the six dyes, which shows that the Cd‐PDNDI could be used as a photocatalytic material for the degradation of dyes. Highlights: A 3D complex Cd‐PDNDI was synthesized.The Cd‐PDNDI show higher degradation efficiency for MG and can be used as a potential photocatalyst.The possible mechanism of in‐situ reaction of ligands in Cd‐PDNDI is proposed, which provides a reference for the further development of NDI series complexes. [ABSTRACT FROM AUTHOR]

Metal-organic frameworks [Co(Hbidc)(H2O)2] (1) and [Mn(Hbidc)(H2O)] (2), with multidentate 1H-benzimidazole-5,6-dicarboxylic acid (H3bidc) ligand, have been synthesized under hydro/solvothermal conditions and structurally characterized by elemental analysis, IR spectrum, and single-crystal X-ray diffraction. Single-crystal X-ray diffraction analysis revealed that the center Co atom of complex 1 is six-coordinated with three-dimensional supramolecular structure and center Mn of complex 2 is five-coordinated with exhibiting a 2D layered network. The photodegradation of Crystal violet dye and Methylene blue dye were studied firstly by complexes 1 and 2 as photocatalysts. Research result indicates that the degradation rate for complex 1 can reach 89.85% , 90.6% and that for complex 2 can reach 88.28% , 79.48%. At the same time, corresponding to photocatalytic kinetics was performed. [ABSTRACT FROM AUTHOR]

[Cu2(UO2)4(suc)4(pac)4] (1), [(Cu(H2O)2)(4,4′-bipy)2][(UO2)2(H2O)2(Hca)2]·3H2O (2), and [(Cu(H2O)2)(UO2)(bta)]·4H2O (3) were synthesized by the reaction of succinic acid and 3-pyridinecarboxylic acid, citric acid and 4,4′-bipyridine, or 1,2,4,5-benzenetetracarboxylic acid ligands with Cu(NO3)2·3H2O and UO2(CH3COO)2·2H2O. The complexes were characterized by IR and UV–vis spectroscopy, powder X-ray diffraction, single-crystal X-ray diffraction, and photoluminescence spectroscopy. Photocatalytic activities of the complexes were also investigated. [ABSTRACT FROM PUBLISHER]

Two new copper complexes, [Cu2(L1)(dipic)2(H2O)2]⋅2H2O (1) and [Cu2(L2)(dipic)2(H2O)2]⋅3H2O (2) (L1 = 1,4-bis((1H-pyrazol-1-yl)methyl)benzene; L2 = 1,4-bis((3,5-dimethyl-1H-pyrazol-1-yl)methyl)benzene; and H2dipic = 2,6-pyridinedicarboxylic acid), were synthesized by the reaction of copper salt, arene-linked pyrazolyl methane ligands, and 2,6-pyridinedicarboxylic acid in 95% C2H5OH. They were characterized by elemental analysis, IR, UV–vis, single-crystal X-ray diffraction analysis, X-ray powder diffraction, and thermogravimetric analysis. We explored the application of the copper complexes in bromination reactions; the complexes exhibited bromination catalytic activity in single-pot reaction for the conversion of phenol red into bromophenol blue. A feasible bromination reaction mechanism of copper complexes was proposed. Two new copper complexes, [Cu2(L1)(dipic)2(H2O)2]⋅2H2O (1) and [Cu2(L2)(dipic)2(H2O)2]·3H2O (2) (L1 = 1,4-bis((1H-pyrazol-1-yl)methyl)benzene; L2 = 1,4-bis((3,5-dimethyl-1H-pyrazol-1-yl)methyl)benzene; and H2dipic = 2,6-pyridinedicarboxylic acid), have been synthesized. The application of the copper complexes in bromination reaction was explored, and a mechanism was proposed. [ABSTRACT FROM AUTHOR]

By introducing 2,6-bis(2-benzimidazolyl)pyridyl and 2,6-di-(pyrazol-3-yl)pyridine derivatives as ligand in the reaction system, three new transition-metal coordination complexes have been successfully synthesized, namely, [Co(HL1)2] ( 1), [Ni(HL1)2] ( 2), and [Ni3(H2L2)2 ⋅(HL2)2] ⋅(OH)3 ⋅(Ac) ⋅H2O ( 3) (H2L1=2,6-bis(benzimidazol-2-yl)pyridine and H2L2=2,6-di-(5-phenyl-1 H-pyrazol-3-yl)pyridine). They are all characterized by elemental analysis, IR spectroscopy, UV absorption spectroscopy, thermogravimetric analysis, powder X-ray diffraction, and single-crystal X-ray diffraction. Structural analysis shows that the structures of complexes 1 and 2 are similar. They are constructed from one metal (Co, Ni) atom and two 2,6-bis(benzimidazol-2-yl)pyridine ligands (HL1−); the HL1− ligand is in the tridentate coordination mode with N3 donors. Complex 3 is a trinuclear Ni complex with four 2,6-di-(5-phenyl-1 H-pyrazol-3-yl)pyridine (H2L2) ligands, in which the H2L2 possesses two coordination fashions: terminal tridentate and bridging tetradentate. In addition, the surface photovoltage spectroscopy and photocatalytic activities of complexes 1- 3 were investigated in detail. The results reveal that complex 3 possesses higher photocatalytic activity. [ABSTRACT FROM AUTHOR]

Solvothermal reaction of uranyl acetate and succinic acid in DMF resulted in formation of three uranyl coordination polymers, [(UO2)4(μ2-OH)7(OH)6]·2(H2O)·(H3O)·4NH2(CH3)2(1), [(UO2)(μ2-OH)(OH)3]·2NH2(CH3)2] (2), and [(DMF)2(UO2)(μ2-OH)4(UO2))] (3). The products were characterized by elemental analysis, IR spectroscopy, X-ray single crystal, and powder diffraction. Structural analysis shows that1is a layer,2and3are 3-D network structures. [ABSTRACT FROM PUBLISHER]

Vanadium complexes (VO)2(2,2′-bipy)2(bta)(H2O)2(1) and (VO)2(1,10-phen)2(bta)(H2O)2(2) (H4bta = 1,2,4,5-benzenetetracarboxylic acid, 2,2′-bipy = 2,2-bipyridine and 1,10-phen = 1,10-phenanthroline) have been synthesized by the reaction of V2(SO4)3, H4bta, 2,2′-bipy (for1) and 1,10-phen (for2) by hydrothermal methods. The complexes were characterized by elemental analysis, IR, UV–vis, thermogravimetric analyses, and single-crystal X-ray diffraction. Structural analyses indicate that1and2are both VO-bta-N-heterocycle system complexes. The central vanadium is coordinated by N2O4donors to form a distorted octahedral geometry. The complexes exhibit catalytic bromination activity in a single-pot reaction with conversion of phenol red to bromophenol blue in a mixed solution of H2O-DMF at 30 ± 0.5 °C with pH 5.8, indicating that they can be considered as a functional model of vanadium-dependent haloperoxidases. The practical application of H2O2detection has also been studied. Two oxovanadium complexes, (VO)2(2,2′-bipy)2(bta)(H2O)2(1) and (VO)2(1,10-phen)2(bta)(H2O)2(2) (H4bta = 1,2,4,5-benzenetetracarboxylic acid, 2,2′-bipy = 2,2-bipyridine and 10-phen = 1,10-phenanthroline), have been synthesized and characterized. The catalytic bromination activity and the practical application of H2O2detection have been studied. [ABSTRACT FROM AUTHOR]

Highlights: [•] Uranyl complexes constructed by 1, 2, 4, 5-benzenetetracarboxylic acid. [•] Disscussing the surface photovoltage spertra. [•] Disscussing the photocatalytic property and the impact factors of the property. [Copyright &y& Elsevier]

Two U(VI)-containing coordination polymers, (UO2)2O2(Suc)(2,2′-bipy)2 (1) and UO2(BC)2(DMF) (2) (2,2′-bipy = 2,2′-bipyridine, H2Suc = succinic acid, HBC = benzoic acid, DMF = N,N-dimethylformamide), have been synthesized and characterized via elemental analysis, infrared spectroscopy, UV-Vis spectroscopy, and single-crystal X-ray diffraction. Structural analyses show that 1 is a 1-D chain coordination polymer in which U(VI) ions are connected by succinic acid ligand and the 1-D chain is connected into a 3-D supramolecular network by C⊟H···O hydrogen bonds between carbon of 2,2′-bipyridine and uranyl oxygen. For 2, monomeric entities are further assembled into a 1-D supramolecular network by C–H···O hydrogen bonds between carbon of DMF molecule and coordinated carboxylate oxygen. Thermogravimetric analyses and photoluminescent properties of 1 and 2 are discussed. [ABSTRACT FROM PUBLISHER]

Two new lanthanide coordination polymers, [Sm(nic)(ad)(HO)(μ-O)] ( 1), [Pr(nic)(ad)]·2HO ( 2) (nic = nicotinic acid, ad = adipic acid) have been synthesized hydrothermally from the self-assembly of the lanthanide ions (Ln) with rigid nicotinic acid and the flexible adipic acid. They were characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. Structural analyses reveal that both of the complexes crystallize in triclinic, space group P- 1 and have different framework characterization. Because of different coordination modes of nicotinate, complexes 1 and 2 exhibit 2D and 3D framework structure, respectively. In 1, the Sm1 and Sm2 atoms and their corresponding centrosymmetric atoms are connected by bridging oxygen atoms to form a 1D Sm(μ -O) polymeric chain along [010] direction. The photoluminescent properties of 1 and thermogravimetric analysis of 1 and 2 are discussed in detail. [ABSTRACT FROM AUTHOR]

Two new 3-D lanthanide coordination polymers, [CeK(btec)(H2O)2] n (1), [Ho(btec)0.5(ad)0.5(H2O)] n (2) (H4btec = 1,2,4,5-benzenetetracarboxylic acid, H2ad = adipic acid), have been synthesized under hydrothermal conditions and characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction. Structural analyses reveal that both complexes crystallized in monoclinic space group P21/c and possessed 3-D net-structures. In 1, btec adopts two types of coordination modes: µ12–η2:η2:η2:η1:η2:η2:η2:η1 bridging mode linking six Ce(III) ions and six K+ ions and the other µ8–η1:η2:η2:η1:η1:η2:η2:η1 bridging mode connecting four Ce(III) ions and four K+ ions. In 2, btec adopts a µ6-bridging with each carboxylate group of btec ligand in a µ2–η1–η2 mode, the adipate is µ4-bridging with each carboxylate µ2–η1–η1-monodentate. The topological analysis shows that 1 can be simplified to a 3-nodal net with the Schläfli symbol {32,48,53,62}4{34,412,512}{438,626,82} and 2 can be simplified to a 3-nodal network with the Schläfli symbol {42,84}{46,66,83}{47,63}2. The thermogravimetric analyses and the X-ray powder diffraction of 1 and 2 are discussed. [ABSTRACT FROM AUTHOR]

Abstract: Two three-dimensional (3D) novel lanthanide complexes with the H2Lzole-5,6-dicarboxylate [Ln2L3(H2O)] [Ln=Eu (1), Tb (2)] and one two-dimensional (2D) novel lanthanide complex [Pr(L)(HL)H2O]·H2O (3) were synthesized by hydrothermal reaction at 180°C and characterized by elemental analysis, infrared spectra and single-crystal X-ray diffraction. The result showed that complexes 1 and 2 are isostructural and build porous 3D networks by L2− groups linking Ln(III) atoms via tetradentate (bridging and bridging) and pentadentate (bridging/chelating and bridging) coordination modes. Complex 3 is a eight-coordinated Pr(III) chain complex, exhibiting a 2D polymeric network with parallel Pr-carboxylate chains along the crystallographic c-axis. In addition, it is found that in these structures, coordination modes of L2− and HL− are versatile and can adopt different conformations according to distinct dimensions of polymeric structures. The photoluminescent properties of 1, 2 and thermogravimetric analyses of the three complexes were discussed in detail. [Copyright &y& Elsevier]

Complexes of melamine with adipic acid and Cu(CH3COO)2 · H2O, [Cu2(MA)(ad)2] · H2O (1), and (MA) · (H2ad) · H2O (2) (MA = melamine; H2ad = adipic acid) have been synthesized under hydrothermal conditions and characterized by elemental analysis, infrared, UV-Vis, and single crystal X-ray diffraction. Both crystallized in the triclinic space group P-1. In 1, MA and adipate bond to copper to construct a 3-D supramolecular framework in an unusual noninterpenetrated pseudo-primitive cubic topology constructed from a four-connected binuclear Cu(II) secondary building unit. A variety of intra- or inter-molecular hydrogen bonds exist. In 2, the 3-D supramolecular structure is formed through strong interactions among MA, adipic acid, and lattice water. Thermal analysis, photoluminescence, and calculations were also performed. [ABSTRACT FROM AUTHOR]

Abstract: Three new oxidovanadium complexes as potential functional model vanadium-dependent haloperoxidases: [VO2(C9H7NO3)](C10H10N2)0.5 (1), [VO(C10H8N2)(C9H7NO3)]3 (2) and [VO(C12H8N2)(C9H7NO3)]·2.33H2O (3) have been designed and synthesized under room temperature with mixed solution of CH3OH and H2O. All the complexes have been characterized by elemental analysis, IR spectra, UV–vis spectroscopy and X-ray single crystal diffraction. The structural analysis indicates that the three complexes are all containing a tridentate amino-Schiff-base (salicylideneglycinate) with imine nitrogen, phenoxyl, and carboxyl oxygen as three donor atoms. The asymmetric unit of complex 1 is formed by one [VO2(C9H7NO3)]– anion and half of (C10H10N2)2+ cation, in which the nitrogen atoms of 4,4′-bipy were protonated. For complex 1, the coordination environment of the central vanadium atom is almost ideal square pyramid, while for complexes 2 and 3, the vanadium atom is a six-coordinated and in a distorted octahedral environment. It is found that there are a variety of inter- and intra-molecular hydrogen bonds in all the three complexes. What is intriguing to us is that the oxidation state of the central metal atom in complex 1 is different from that of complex 2 and 3: the oxidation state of vanadium in complex 1 is +5, while ones in complex 2 and 3 are +4. Bromination reaction activity of the complexes has been evaluated by the method with phenol red as organic substrate in the presence of H2O2, Br– and phosphate buffer, indicating that they can be considered as potential functional model vanadium-dependent haloperoxidases. In addition, thermal analysis, cyclic voltammetry and quantum chemistry calculations were also performed and discussed in detail. [Copyright &y& Elsevier]

Three new transition metal complexes, [FeII(H2O)6][(C9H7NO3)2FeII] · H2O (1), H[K(H2O)3][(C9H7NO3)2CoII] · H2O (2), and [CoII(H2O)6][(C9H7NO3)2CoII] · H2O (3), with salicylideneglycine have been synthesized and characterized by elemental analysis, IR spectra, UV-Vis spectroscopy, and X-ray crystallography. The structure analyses indicate that the tridentate salicylideneglycine binds through aliphatic nitrogen, phenoxy, and carboxylic oxygen in the anion. There are many inter- and intra-molecular hydrogen bonds among lattice water, the anion, and the cation to form a 3-D network. The thermogravimetric analyses and the quantum chemistry calculations of compounds 1, 2, and 3 are also discussed. [ABSTRACT FROM AUTHOR]

Abstract: A series of new lanthanide coordination polymers, with the formula [Ln(Suc)0.5(p-BDC)] (Ln=Eu (1), Sm (2), Tb (3), Pr (4), Ho (5); H2Suc=succinic acid; p-H2BDC=1,4-benzene dicarboxylic acid), have been synthesized under hydrothermal condition and all of them have been structurally characterized. X-ray diffraction analyses reveal that complexes 1–5 are isostructural and crystallized in orthorhombic space group Pbca. One-dimensional infinite inorganic edge-sharing polyhedra chains formed by lanthanide ions and tetradentate carboxyl groups of succinic acid ligands, link to each other through the carbon atoms of succinic acid ligands and phenyl groups of the 1,4-benzene dicarboxylic acid ligands, to lead to a three-dimensional framework structure. In addition, the phase purities of the bulk samples were identified by X-ray powder diffraction. The photoluminescent properties of 1 and 3 were discussed in detail. [Copyright &y& Elsevier]

A new copper(II) complex of general formula Na2(Cu3L4) · 2H2O · 2CH3OH (L = 5-phenyl pyrazole-3-carboxylic acid) has been newly obtained by the reaction of copper chloride with 5-phenyl pyrazole-3-carboxylic acid in methanol in the presence of NaOH at room temperature. X-ray diffraction analysis of the crystal structure reveals that the complex is a trinuclear crystal structure that consists of two sodium cations and an anion cluster. Two kinds of coordination modes were observed in the Cu center of the anion cluster; the Cu1 is coordinated to four nitrogen atoms from four 5-phenyl pyrazole-3-carboxylic acid ligands, forming a distorted tetrahedral (CuN4) geometry, while Cu2 is coordinated to two oxygen atoms and two nitrogen atoms of two 5-phenyl pyrazole-3-carboxylic acid, respectively, forming a slightly distorted square planar (CuN2O2) geometry. Cu and Cu are connected by four nitrogen of two different ligands, while Cu and Na are linked by carboxyl oxygen atom from the ligand. The Cu atoms and Na atoms are connected furthermore each other by carboxyl oxygen atom, forming a three-dimensional structure. [ABSTRACT FROM AUTHOR]

Rare-earth dicarboxylate open structure materials {[Pr(H2O)]2[O2C(CH2)2CO2]3}n (1) and {[Pr(H2O)]2[O2C(CH2)2CO2]3 · H2O}n (2) have been synthesized by reaction of succinic acid with nitrate salts of Pr(III) under hydrothermal conditions (150°C, 4 days). Complex 1 crystallizes in the triclinic space group [image omitted] with a = 7.8828(8) Å, b = 8.1247(8) Å, c = 14.2271(14) Å, α = 96.907(2)°, β = 96.962(2)°, γ = 103.600(2)°, and Z = 2. Complex 2 is in the monoclinic space group C2/c with a = 20.104(4) Å, b = 7.9343(16) Å, c = 14.013(3) Å, β = 121.08(3), and Z = 4. X-ray diffraction analysis reveals that the complexes are constructed by succinic acid bridging the chains of edge-sharing PrO8(H2O) polyhedra to form 3D network structures. 1 and 2 possess different topological structures due to the difference in the conformations of coordinated succinic acid. Thermal decomposition kinetics of 1 and 2 are also discussed in detail. Non-thermal kinetic decomposition shows that, for 1, the possible reaction mechanisms of the three steps are three dimensional pervasion with n = 2, nucleation and growth with n = 1/4, nucleation and growth with n = 1/4, respectively, and the kinetic equations may be expressed as dα/dT = (A/β)exp(-E/RT){3/2(1 - α)2/3[1 - (1 - α)1/3]-1}, dα/dT = (A/β)exp(-E/RT){1/4(1 - α)[-ln(1 - α)]-3}, and dα/dT = (A/β)exp(-E/RT){1/4(1 - α)[-ln(1 - α)]-3}, respectively; for 2, the possible reaction mechanisms of the three steps are nucleation and growth with n = 1/4, chemical reaction, nucleation and growth with n = 1. Kinetic equations may be expressed as dα/dT = (A/β)exp(-E/RT){1/4(1 - α)[-ln(1 - α)]-3}, dα/dT = (A/β)exp(-E/RT)[(1 - α)2], and dα/dT = (A/β)exp(-E/RT)(1 - α). [ABSTRACT FROM AUTHOR]

Abstract: Two new oxovanadium (IV) complexes VO(HB(pz)3)(H2B(pz)2) (1) and VO(B(pz)4)2 (2) have been obtained by the reaction of oxovanadium sulfate with the corresponding ligands KHB(pz)3, KH2B(pz)2 and KB(pz)4, respectively. The two complexes were characterized by elemental analyses, IR, UV–Vis and X-ray diffraction. Complex 1 crystallizes in the orthorhombic space group, Pca21. Complex 2 crystallizes in the orthorhombic space group, Pna21. In both complexes, five nitrogen atoms and one oxygen atom coordinate to the vanadium atom, forming a distorted octahedral geometry (VON5). In addition, related spectra characterization, hydrogen-binding properties, structural configuration and quantum chemistry calculations are also discussed. [Copyright &y& Elsevier]

Reaction of a mixture of CuCl2, Ni(CH3COO)2 and NaH2B(pz)2 in methanol solution, resulted in the dihydrobis(pyrazolyl)borate complexes Cu(H2B(pz)2)2 and Ni(H2B(pz)2)2, respectively. Complexes 1 and 2 were characterized by IR, elemental analyses, thermal analyses and X-ray diffraction. The two complexes both crystallize in the space group Pbca, with crystal parameters for complex 1a = 14.443(3) Å, b = 6.2162(12) Å, c = 17.865(4) Å, α = β = γ = 90°, V = 1604.0(5) Å3, Z = 4; for complex 2a = 14.5264(4) Å, b = 6.3235(2) Å, c = 17.4720(4) Å, α = β = γ = 90°, V = 1604.94(8) Å3, Z = 4, respectively. X-ray structure analysis has shown that complexes 1 and 2 are both monomeric neutral complexes, and possess similar coordination modes around the metal centers. [ABSTRACT FROM AUTHOR]

V(IV)O(H 2 O) 2 (2,6-pyridinedicarboxylate)·2H 2 O ( 1 ) was obtained by the reaction of VO(acac) 2 with 2,6-pyridine dicarboxylic acid in MeOH and water. Complex ( 1 ) was characterized by IR spectroscopy, element analysis and X-ray diffraction. It crystallizes in space group P . X-ray structure analysis has shown that complex ( 1 ) is a monomeric neutral complex containing vanadyl ion, 2,6-pyridinedicarboxylate ligand and coordinated water, possessing distorted octahedral geometry. Complex ( 1 ) is constructed from mononuclear vanadium, V(IV)O(H 2 O) 2 (2,6-pyridinedicarboxylate) units and crystallization water molecules held together in an extensive two-dimensional network via O-H···O hydrogen bonds, π-π stacking interactions between parallel aromatic pyridines, and face-to-face stacking interactions between parallel carbonyl groups of 2,6-pyridine dicarboxylic acid ligands along the plane formed by the x , z axis of the unit cell. [ABSTRACT FROM AUTHOR]

Two new coordination complexes based on benzimidazole dicarboxylic acid, Zn(Hbidc)⋅H2O (1) and Cd(Hbidc)(H2O) (2), have been synthesized under hydrothermal conditions. The complexes were characterized using elemental analysis, infrared and UV–visible spectroscopies, powder X‐ray diffraction, thermogravimetry and single‐crystal X‐ray diffraction. Structural analyses showed that the crystal structures of 1 and 2 are different, due to the various modes of linking of the benzimidazole dicarboxylic acid. Complex 1 has a two‐dimensional network structure and 2 has a three‐dimensional network structure. In addition, we studied the performance of the fluorescence response of two complexes. Results showed that the complexes can be used as chemical sensors for multifunctional testing, such as for UO22+, xanthine and Fe3+ ions. Even if the concentration is very low, they could also be detected, showing that coordination complexes 1 and 2 have very high fluorescence sensitivity. The detection limit for UO22+ is 5.42 nM (1) and 0.02 nM (2), that for xanthine is 1.37 nM (1) and 0.28 nM (2), and that for Fe3+ ions is 0.76 nM (1) and 0.62 nM (2). [ABSTRACT FROM AUTHOR]

Highlights: [•] Three transition metal complexes with pyridine-based ligand and dicarboxylate acids are synthesized. [•] Crystal structures are given. [•] Their activities in surface electron behavior field have been discussed. [ABSTRACT FROM AUTHOR]

Abstract: A new series of rigid–flexible lanthanide coordination polymers, namely, [Eu(BSA)(glu)(H2O)2]·H2O (Ln=Eu(1), Sm(2), Ce(3), Pr(4), Nd(5)); H2glu=glutaric acid, HBSA=benzene sulfonic acid), have been constructed by a solution synthesis method from the self-assembly of the lanthanide ions (Ln3+) with the flexible aliphatic dicarboxylate glutaric and the rigid aromatic benzene sulfonic acid. All of them were characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction. X-ray single crystal analyses reveal that they crystallize in monoclinic, space group P2 1/n, possessing 2D net-structures. In addition, the phase purities of the bulk samples were identified by X-ray powder diffraction. The thermogravimetric analysis of 1 and photoluminescent properties of 1 and 2 were investigated in detailed. [ABSTRACT FROM AUTHOR]

Abstract: The reactions of (NH4)2WS4 and three polycarboxylate ligands (including nitrilotriacetate (nta3−), citrate (Hcit3−) and ethylenediaminetetraacetate (EDTA4−)) in H2O/EtOH at ambient temperature have resulted in three new trioxotungsten (VI) complexes, K3[WO3(nta)]·H2O 1, (NH4)4[WO3(cit)]·2 H2O 2 and K2(NH4)2[W2O6(EDTA)]·4H2O 3, respectively. These three complexes have been characterized by IR, XPS, TGA–DTA, 1H and 13C NMR spectroscopy. And their structures have been determined by X-ray crystallographic studies, which confirm that 1 and 2 are mononuclear compounds and 3 is a binuclear compound. Each tungsten atom in 1–3 is coordinated to three unshared oxygen atoms, which adopt fac stereochemistry, while the remaining fac positions are occupied by three atoms from the ligands. The electrochemical properties of 2 and 3 have been investigated. [Copyright &y& Elsevier]

The complex 1 was synthesized by HL 1 and Co(II), which forms a one-dimensional double-chain supermolecular structure through inter-molecular hydrogen. The complex 2 synthesized by H 4 L 2 and Cu(II), which forms a three-dimensional network structure with multiple channels. The catalytic reduction experiments show that the efficiency of complexes 1 and 2 on p-Nitrophenol is greater than 96%, which has potential catalytic application value. [Display omitted] • Constructed two novel complexes 1 and 2 , characterized by spectroscopy and single crystal X-ray crystallography in detail. • The complex 1 formed a one-dimensional double-chain supermolecular structure through intermolecular hydrogen and complex 2 formed three-dimensional network structure with multiple channels. • The catalytic reduction experiments of complexes 1 and 2 towards p-Nitrophenol were carried out preliminary and analysis of the mechanism of catalytic reduction of p-Nitrophenol. Nitrogen heterocyclic polycarboxylic acid is a type of ligands with excellent coordination ability and rich conformations. Two metal complexes, ([Co 2 (L 1) 2 (CH 3 COO)(H 2 O) 3 ]‧(CH 3 COO)‧H 2 O (1) (HL 1 = 4-[2,6-bis(pyrazin-2-yl) pyrid-4-yl]benzoic acid)) and (Cu 2 (L 2)(H 2 O) (2) (H 4 L 2 = 5-[6-(3,5-dicarboxy phenylamino)pyrid-2-ylamino]benzene-1,3-dicarboxylic acid)) were synthesized with transition metal salts and nitrogen heterocycle polycarboxylic acid ligands by solvothermal method. Both complexes were characterized by infrared and ultraviolet spectroscopy, powder X-ray diffraction analysis, and thermogravimetric analysis. The X-ray single crystal structural analysis shows that complex 1 is a one-dimensional double-chain supramolecular structure built by intermolecular hydrogen bonds. While complex 2 is a three-dimensional framework with multiple channels, where the two independent Cu(II) metals are five-coordinated to form a square pyramidal coordination geometry. In addition, in order to investigate the functional properties of the two complexes, catalytic reduction experiments towards p-nitrophenol were carried out preliminarily. The reduction efficiency above 96 % demonstrates their potential as catalysts. [ABSTRACT FROM AUTHOR]

Graphical abstract Three new superoxide dismutase mimetics with perfect SOD activity were discovered. Their IC 50 values were less than the internationally specified values (30 mg/L). Particular, the IC 50 value of Cd-SOD is 2.7 mg/L. Highlights • Three new superoxide dismutase model compounds: [CoL(H 2 O)]·2H 2 O (1), [CdL(H 2 O)]·H 2 O (2) and [PbL] (3). • Superoxide dismutase (SOD) activity. • Relationship between structure and SOD activity. Abstract Three new superoxide dismutase model compounds: [CoL(H 2 O)]·2H 2 O (1), [CdL(H 2 O)]·H 2 O (2) and [PbL] (3) were successfully synthesized by the reaction of a transition metal salt and 5-aminoisophthalic acid under hydrothermal conditions (L: 5-aminoisophthalic acid). The three compounds were characterized by elemental analysis, infrared spectroscopy, ultraviolet–visible spectroscopy, PXRD analysis and TG analysis. X-ray single crystal diffraction analysis showed that compounds 2 and 3 were 3D inorganic–organic framework structures while compound 1 was a 2D structure. These simulations contained pores structures with maximum sizes of 4.08–14.67 Å. To further explore the functional properties of these compounds, we firstly analyzed their SOD activity, and the results demonstrated that they have different SOD activities. The IC 50 values of the three mimics are much smaller than the international standard for SOD standards, demonstrating that these mimics have superior Reactive Oxygen Species resistance. [ABSTRACT FROM AUTHOR]

Three novel transition metal complexes, [Co(L)(Cl)(H 2 O)]·3H 2 O ( 1 ), [Cu(L) 2 ]·5H 2 O ( 2 ) and [Ni(L) 2 ]·8H 2 O ( 3 ) were synthesized at hydrothermal conditions based on ligand (HL: 2,6-bis(2-pyrazinyl)pyridine-4-benzoic acid) and transition metal Co(II), Cu(I), Ni(II) salts. All the complexes were characterized by elemental analysis, IR spectroscopy, UV–Vis spectroscopy and powder X-ray diffraction (PXRD). The X-ray single crystal diffraction showed that complexes 1 and 2 are 2D planar structures and complex 3 is a 1D chain structure. In addition, we investigated the photocatalysis performance of the complexes 1 – 3 , which degraded organic dyes methylene blue (MB) under UV–Vis irradiation. According to the experimental phenomenon, compared with the other complexes, complex 1 achieved a higher photocatalytic activity, after photocatalyzing for 80 min, the degradation rate of dye is as high as 96%. [ABSTRACT FROM AUTHOR]

Four new complexes, [Cd(L 1 )(NO 3 ) 2 (H 2 O)] ( 1 ), [Co(L 1 )Cl 2 ]·(CH 3 ) 2 CO ( 2 ), {[Cu(L 1 )(μ-Cl) 2 CuCl 2 ]·H 2 O·CH 3 CN} n ( 3 ) and [Ni(L 1 ∗ ) 2 (H 2 O) 2 ]·4H 2 O ( 4 ), were synthesized at room temperature or hydrothermal conditions based on triazine-pyrazole ligand L 1 and L 1 * and transition metal Co (II), Ni (II), Cu (II) and Cd (II) salts. (L 1 : 2,4,6-tri(3,5-dimethyl-pyrazol-1-yl)-1,3,5-triazine; L 1 *: 6-(3,5-Dimethyl-2,5-dihydro-pyrazol-1-yl)-2,4-dione-1,3,5-triazine) The structures of all complexes were determined by elemental analysis, IR spectra, UV spectra and TG analysis. Through the X-ray single crystal diffraction showed that complexes 1 and 2 are 1D chain structures, complex 3 is a 3D network structure and complex 4 is a 2D network structure. In addition, the surface photovoltage spectroscopy (SPS) and electric-field-induced surface photovoltage spectroscopy (EFISPS) results indicate that all complexes can be used as p -type semiconductor. Furthermore, we investigated also the performance of the some complexes in the degradation of organic dyes RhB under UV irradiation. According to observe the experimental phenomenon, it is found that the tested complexes have different certain degree of photodegradation performances. Its photocatalytic effect is better than that of only hydrogen peroxide being involved in the reaction system under the same conditions. [ABSTRACT FROM AUTHOR]

• A 3D supramolecular layered MOF Bi-BDC was synthesized. • Higher degradation efficiency of Bi-BDC for both anionic and cationic dyes. • Bi-BDC can degrade mixed dyes simultaneously. A self-assembled Bi-MOF {[Bi(BDC) 1.5 (DMF)(H 2 O)]·DMF} n (Bi-BDC) (H 2 BDC = terephthalic acid, DMF = N , N-dimethylformamide) was designed and synthesized by the reaction of bismuth nitrate and H 2 BDC under solvothermal conditions. The basic structure of the complex was characterized by elemental analysis, infrared spectroscopy, UV–vis spectroscopy, PXRD, single crystal X-ray diffraction and thermogravimetric analysis. The structure analysis shows that the Bi-BDC has a three-dimensional supramolecular layered network structure by p - π interaction. In addition, the properties of the Bi-BDC on photocatalytic degradation of organic dyes were investigated. Surprisingly, it has superior degradation rate for both anionic and cationic dyes with a very short time by adding hydrogen peroxide. Furthermore, the kinetic analysis, degradation of mixed dyes, recycle experiments and catalytic mechanism were investigated. The results show that Bi-BDC has potential application value in photocatalytic degradation of organic dyes in future. [Display omitted] [ABSTRACT FROM AUTHOR]

Two complexes {[Cd 3 (1,10-phen) 3 (HL) 3 ]·4.5H 2 O ( 1 ) and Co(1,10-phen) 2 (H 2 L) 2 ( 2 ) {H 3 L = 5-((4-carboxybenzyl)oxy)isophthalic acid, 1,10-phen = phenanthroline)} based on the rigid–flexible mixed tripodal ligand 5-((4-carboxybenzyl)oxy)isophthalic acid were synthesized in the presence of auxiliary ligands under hydrothermal condition. The single crystal X-ray diffraction analysis revealed that complexes 1 and 2 exhibited a one-dimensional framework and a clustered structure, respectively, while both the complexes presented three-dimensional supermolecular network structures at last by the interaction of the hydrogen bonds. Both of complexes 1 and 2 were characterized by elemental analysis, IR spectroscopy, the single crystal X-ray diffraction analysis, and thermogravimetric analysis. In addition, the surface photovoltage spectroscopy (SPS) and electric-field-induced surface photovoltage spectroscopy (EFISPS) showed that complexes 1 and 2 could behave as p -type semiconductors. The photoluminescent (PL) results showed that complex 1 displayed high-sensitivity luminescent sensing function for nitrobenzene. [ABSTRACT FROM AUTHOR]

A series of coordination oxidovanadium(IV) complexes: [VOSO 4 (bpz-eaT)]·C 4 H 6 O 4 ( 1 ), [VOSO 4 (bpz-eaT)]·0.5(C 10 H 18 O 4 ) ( 2 ) and [VOSO 4 (bpz-eaT)]·C 5 H 8 O 4 ·CH 3 CN ( 3 ) (bpz-eaT = 2,4-bis (3,5-dimethyl-1H-pyrazol-1-yl)-6-diethylamino-1,3,5-triazine) were synthesized in MeCN. All of the complexes are characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction. The single-crystal X-ray diffraction analyses reveal that the vanadium atoms are six-coordinated in all complexes. In the study of Cyclohexane (Cy) oxidation, promoted by our complexes, the effects of the amount of H 2 O 2 and HNO 3 were investigated. It was found that complex 3 exhibited the highest catalytic activity in MeCN at 9 h, 60 °C, which is the first oxidovanadium(IV) complex catalyst that we found can catalyze Cy produce more cyclohexanone (CyO) than cyclohexanol (CyOH) oxidated by H 2 O 2 . [ABSTRACT FROM AUTHOR]

A series of 3d–4f heterobinuclear complexes were constructed by employing the 2,2′-bipy (2,2′-bipy = 2,2′-bipyridine) ligand and corresponding metal ions (M II /Ln III , M = Co II , Cu II and Zn II ; Ln III = Nd III , Sm III , Eu III and Tb III ). Elemental analyses, IR, UV–vis–NIR spectra, PXRD and single crystal X-ray diffraction analysis reveal that complexes 1 – 4 , 5 – 8 , and 9 – 12 are isomorphous, respectively. The zero-dimensional structures are further connected to 2D or 3D supramolecular network structures via extensive intermolecular hydrogen bonds. Luminescence studies for the heterobinuclear complexes containing Sm III , Eu III and Tb III reveal that the chromophoric composed of Zn II /L may efficiently sensitize the luminescence of the rare earth cations which acts as an antenna, whereas the existence of Cu II leads to the quenching of the luminescence of Ln III ions. [ABSTRACT FROM AUTHOR]

Molecular design and efficient synthetic procedures have been developed for pyrazole and its derivatives with different linkers. In particular, twelve compounds with –I or –NO 2 substituted groups on the pyrazole ring were synthesized for the first time. These compounds are characterized by element analysis, IR, HNMR, M.P. and X-ray diffraction. In addition, some compounds and corresponding complexes were also assayed in vitro for their ability to inhibit the growth of representative Gram-positive bacteria, Gram-negative bacteria and the fungus. It was worthwhile to note that some compounds could be used as potential antibacterial agents. [ABSTRACT FROM AUTHOR]

Copper complexes [Cu 2 (μ 2 -C 2 O 4 )(HC 2 O 4 )(L 1 )]·(H 2 C 2 O 4 ) (1), [Cu 2 (Bpz ∗ T-OEt) 2 Cl 2 CuCl 4 ] (Bpz ∗ T-EtOH = L 2 ) ( 2 ) and [Cu 2 (Bpz ∗ T-O) 4 ]·4pz ∗ ·4H 2 O ( 3 ) (Bpz ∗ T-O = L 3 ) (L 1 = 2,4-bis(3,5-dimethyl-1 H -pyrazol-1-yl)-6-diethylamino-1,3,5-triazine, Bpz ∗ T = 2,4,6-tri(3,5-dimethylpyrazol-1-yl)-1,3,5-triazine) have been synthesized in the reaction of Cu(Ac) 2 ·2H 2 O, oxalic acid, L 1 (for 1 ) or Bpz ∗ T (for 2 and 3 ) and CuCl 2 ·2H 2 O with solution methods. They were characterized by elemental analysis, IR, UV–Vis and thermogravimetric analyses (TG), and the single-crystal X-ray diffraction analysis. Structural analysis reveals that center metal Cu atoms in the complexes 1 and 3 are six-coordination modes, forming distorted octahedron geometries with N2, O2 and N6 donors, respectively. While Cu atom in the complex 2 is four-coordination and five-coordination modes, forming tetragonal pyramid and tetrahedron geometry with N3 Cl2 and N6, respectively. The complexes exhibit catalytic bromination activity in a single-pot reaction of the conversion of phenol red to bromophenol blue in a mixed system of H 2 O–DMF–KBr at the constant temperature of 30 ± 0.5 °C with a buffer solution of NaH 2 PO 4 –Na 2 HPO 4 (pH 5.8), indicating that they can be considered as a potential functional model of bromoperoxidase. [ABSTRACT FROM AUTHOR]

Experiencing a series of complicated changes, abundant orange crystals of novel metallic phase of vanadium pentoxide were obtained by a mild chemical method, the formula of which is defined as [V 3 ( μ 3 -O) 2 ⋅( μ 1 -OH)⋅O 5 ]⋅H 2 O. Differ from the synthesis methods of vanadium oxide published, we have adopted a simple solution method that mixed starting materials are refluxing in the system of ethanol–water under a relatively lower temperature. Symmetry of the crystals is Monoclinic, with cell unit dimensions: a = 4.9978(10) Å, b = 8.4273(17) Å, c = 7.8669(16) Å, β = 96.44(3)° and space group of P2 1 / m . The structure of the complex was characterized by elemental analysis, IR, UV–vis spectroscopy and single-crystal diffraction analysis. Powder X-ray diffraction (PXRD) was used to detect the purity of the crystals, and crystal morphology was detected by the scanning electron microscope (SEM). In addition, in order to extend application of oxidovanadium complexes, bromination catalytic activity about the complex in a single-pot reaction of the conversion of phenol red to bromophenol blue in a mixed solution of H 2 O–DMF at a constant temperature of 30 ± 0.5 °C with a buffer solution of NaH 2 PO 4 Na 2 HPO 4 (pH = 5.8) was evaluated firstly, indicating that the complex can be considered as a potential functional model of bromoperoxidase, in the meantime, we have conducted the bromination catalytic reaction to simulate and measure the changes in reaction process indirectly. Besides, catalytic oxidation activity of the complex is also evaluated in the oxidation of cyclohexane (Cy) and cyclopentane with hydrogen peroxide promoted under mild conditions, showing potential catalytic activity of the complex by comparing TON (total turnover number) ratios of CyO/CyOH (CyO is the abbreviation of cyclohexanone and CyOH represents cyclohexanol) in the oxidation results. [ABSTRACT FROM AUTHOR]

Highlights: [•] Synthesizing two zinc complexes constructed from indoleacetic acid. [•] Discussing the UV–vis absorption spectra. [•] Discussing the photoluminescent properties of two complexes. [ABSTRACT FROM AUTHOR]

Highlights: [•] Four novel oxidovanadium complexes. [•] Poly(pyrazolyl)borate ligand modified by iodine. [•] Crystal structure. [•] Bromination reaction activity. [•] Potential detection of hydrogen peroxide. [Copyright &y& Elsevier]

Abstract: A series of the p-bis[(1-pyrazolyl)methyl] benzene ligands (L1 –L6 ) in the DMSO system were synthesized. In the mean time, by using the ligands as a linker, a new family of transition metal coordination polymers, namely, [Cu2(L1 )2Cl4] (1), [Cu2(L2 )2Cl4] (2), [Ag(L2 )(NO3)] (3), [Zn2(L2 )2(SCN)4] (4) and [Cd2(L2 )(SCN)4] (5) [L1 =1,4-bis((1H-pyrazol-1-yl)methyl)benzene; L2 =1,4-bis(3,5-dimethyl-1H-pyrazol-1-yl)methyl)benzene] have been constructed by the reaction of the p-bis[(1-pyrazolyl)methyl]benzene and corresponding to the transition metal compounds in a mixed solution of CH3OH/C2H5OH at mild temperature condition. All the coordination polymers and p-bis[(1-pyrazolyl)methyl]benzene ligands were characterized by elemental analysis, IR spectroscopy, 1H NMR and 13C NMR, and some of them were characterized by UV spectroscopy, thermogravimetric analysis, X-ray powder and X-ray single-crystal diffraction. Structural analyses reveal that the ligands L3 –L5 (L3 =1,4-bis((4-iodo-1H-pyrazol-1-yl)methyl)benzene, L4 =1,4-bis((4-iodo-3,5-dimethyl-1H-pyrazol-1-yl)methyl)benzene, L5 =1,4-bis((4-nitro-1H-pyrazol-1-yl)methyl)benzene,L6 =1,4-bis((4-nitro-3,5-dimethyl-1H-pyrazol-1-yl) methyl) benzene) are discrete organic compound molecules and the complexes 1–5 are 1D M–L–M coordination polymers, which are further interlinked via hydrogen bonds resulting in 2D or even 3D supermolecular networks. The luminescent properties of the coordination polymers 3, 4 and 5 were examined by luminescence spectra. The analytic results indicate that different metal complexes with the same ligand have different influence on the characteristic photoluminescence. Furthermore, the cytotoxicity of the ligands L1 –L6 and complexes 1–5 were evaluated against hepG2 cells. For the ligands of L1 –L6 , the different substituents of the pyrazole ring slightly influenced the cytotoxicity of the cell. It is found that nitro-compounds have shown the highest cytotoxicity under the same concentration condition. The cytotoxic activity of the complexes 1–5 are strongly increased by the introduction of the transition metals. [Copyright &y& Elsevier]

Abstract: A new family of aminoacid-derivatized oxidovanadium complexes as potential functional model of vanadium haloperoxidases: [VVO(sal-phe)(OMe) (MeOH)] (1), [VIVO(sal-ala)(2,2′-bipy)]·H2O (2), [VIVO(sal-ala)(1,10-phen)]·0.5H2O (3) and [VIVO(sal-his)(1,10-phen)]·2MeOH (4) (H2sal-phe=Schiff base derived from salicylaldehyde and dl-β-phenylalanine, H2sal-ala=Schiff base derived from salicylaldehyde and dl-α-alanine, H2sal-his=Schiff base derived from salicylaldehyde and l-histidine) have been synthesized. All the complexes were characterized by elemental analysis, IR spectra and UV–Vis spectroscopy. In particular, molecular structures of three representative complexes (1, 2 and 3) were determined by X-ray crystallography. In addition, bromination reaction activity of the starting material and the complexes has been tested by a method with phenol red as organic substrate in the presence of H2O2, Br− and phosphate buffer, the studying results indicate that the vanadium complexes can catalyze the visible conversion of phenol red to bromophenol blue under weak-acid conditions and the different structural characterizations of the complexes exhibit different catalytic activity, therefore, the complexes can be considered as a potential functional model of VHPO. [Copyright &y& Elsevier]

Abstract: Two-dimensional coordination polymers, [M(C8H12O4)(C10H8N2)]·H2O [M=Co (1), Cd (2); C10H8N2 =4,4-bipyridine, C8H14O4 =subaric acid] were obtained from the reaction of the metal salts, bipy and subaric acid at 180°C and characterized by elemental analysis, infrared spectrum, and single-crystal X-ray diffraction and surface photovoltage spectrum (SPS). The single-crystal X-ray diffraction showed that the subaric ligand in the two complexes exhibits two types of modes coordinating to transition metal ions, resulting in the formation of a 1D infinite chain along the c-axis. In addition, the results of SPS for complexes 1 and 2 indicate that these two complexes exhibit positive surface photovoltage responses in the range of 300–800nm, which can be assigned to LMCT and MLCT, respectively. And the SPS of complex 1 also can be assigned to the d→d* electronic transition. The SPS spectra of the two complexes are consistent with their UV–vis spectra. [ABSTRACT FROM AUTHOR]