Inorganic Chemistry Communications (v.15, #C)

Contents List (iii-xxii).

A luminescent compound, [Cd (HO-BDC) (bpe)1.5] n (1 HO-H2BDC=  5-hydroxyisophthalic acid, bpe=1,2-bis (4-pyridyl) ethane), was hydrothermally synthesized. It features a 5-connected two-dimensional (2D) double layer motif. Interestingly, this 2D double layer motif is further interlocked with the neighboring ones in the parallel fashion, giving rise to the final three-dimensional (3D) polycatenated network. Moreover, the title compound exhibits intense yellow photoluminescence at room temperature.Presented here is a novel photoluminescent Cd(II) coordination polymer, [Cd (HO-BDC) (bpe)1.5] n (1 HO-H2BDC=  5-hydroxyisophthalic acid, bpe=1,2-bis (4-pyridyl) ethane), which features a 5-connected two-dimensional (2D) bilayer motif. Interestingly, this 2D bilayer is further interlocked with the adjacent ones, giving rise to a three-dimensional (3D) polycatenated network.Display Omitted► New Cd(II) compound with 5-connected two-dimensional double layer ► New Cd(II) compound features 2D → 3D polycatenated structure ► This compound exhibits intense yellow photoluminescence at room temperature.
Keywords: Luminescent compound; Double layer; Parallel fashion; Polycatenation;

A novel tetranuclear vanadium(IV) complex, [VIV 4O44-O)(μ-OCH3)2(pyCHNO)4·H2O] (1) (pyCHNOH = 2-pyridinaldoxime), was synthesized and characterized. The binding propensity of the complex 1 to calf thymus DNA (CT-DNA) was studied by fluorescence spectroscopy, UV–vis absorption and viscosity measurement. Single crystal X-ray diffraction analysis reveals that the complex 1 possesses centrosymmetric structure and pseudo-tetrahedron conformation. Electrochemical behavior indicates the quasi-reversible nature of the electron-transfer process in the complex 1. The results suggest the groove-binding propensity of the complex 1.A novel tetranuclear vanadium(IV) complex was synthesized and characterized. The electrochemical behavior and DNA binding efficiency were discussed on the basis of X-ray structural analysis.Display Omitted► Employment of a template yields a peculiar tetranuclear vanadium(IV) complex. ► The complex exhibits centrosymmetric and papilionaceous configuration. ► Four vanadium centers form a pseudo-tetrahedron. ► The results suggest the groove-binding nature of the complex.
Keywords: Vanadium; Tetranuclear complex; 2-pyridinaldoxime; Electrochemical behavior; DNA binding;

A new cobalt(II) coordination polymer with azide and a quadritopic ligand, [Co2(N3)4(TPOM)]n (TPOM = tetrakis(4-pyridyloxymethylene) methane), was solvothermally synthesized and characterized structurally and magnetically. The compound exhibits a three-dimensional framework in which Co(II) chains with alternating double end-on (EO) and double end-to-end (EE) azide bridges are linked by the tetrapyridyl ligand in a bowl-shaped conformation. With both Co(II) and TPOM as 4-connecting nodes, the structure represents the first real example of the 4-connected net topology with point symbol {32·104}{32·4·102·11}2. Magnetic studies demonstrated that the alternating double EO and double EE azide bridges induce ferro- and antiferromagnetic interactions along the chain.The first azide-bridged magnetic system derived from a quadritopic organic bridging ligand (TPOM) was obtained. And the alternate double μ-1,1-N3 and double μ-1,3-N3 bridges transmit alternating ferromagnetic and antiferromagnetic interactions between Co(II) ions along the chain.Display Omitted► First azide-bridged magnetic system derived from a quadritopic organic bridging ligand (TPOM). ► A new example of the rare Co(II) systems with alternate double μ-1,1 N3 and double μ-1,3 N3 bridges. ► First real network showing the sqc967 3D topology, resulting from the connection of chains of different directions by TPOM. ► Magnetic properties investigated, revealing alternating ferromagnetic and antiferromagnetic interactions along the chain.
Keywords: Cobalt; Azide; Topology; Magnetic properties;

A novel highly selective colorimetric sensor for Ni(II) ion using coumarin derivatives by Jinqiang Jiang; Chao Gou; Jing Luo; Chenglin Yi; Xiaoya Liu (12-15).
A new coumarin based colorimetric nickel sensor 1 with high selectivity and sensitivity toward Ni2+ ion was reported. The absorption maximum of 1 shows a large red shift from 341 nm to 540 nm (Δ = 200 nm) in the presence of Ni2+ ion, and the resulted color change from colorless to pink upon addition of Ni2+ is very easily observed by the naked eye, while other metal ions, such as Zn2+, Cd2+, Cu2+, Fe3+, Ag+, Pb2+, alkali metal and alkaline earth metal cations do not induce such a change. By the “naked eye”, the detection limit of Ni2+ is as low as 0.5 μM in solution, which is lower than the current American Environmental Protection Agency (EPA) standard for drinking water. As far as we are aware of, this is the first reported colorimetric chemosensor capable of detecting Ni2+ ion.A novel highly selective colorimetric sensor 1 for Ni2+ ion has been reported: (a) absorbance spectra of chemosensor 1 (20 μM) with increasing concentrations of Ni2+ ion in ethanol. Inset: the absorbance at 535 and 341 nm as a function of Ni2+ ion concentration. (b) Photographs of the solution 1 (10 μM) after addition of different concentrations of Ni2+ ion.Display Omitted► A novel coumarin based colorimetric nickel sensor 1 was synthesized. ► Compound 1 shows 200 nm red-shift in absorption spectrum upon coordination with Ni2+ ion. ► The resulted color change from colorless to pink upon addition of Ni2+ ion is easily observed by the naked eye. ► Other metal ions do not interfere. ► This is the first reported colorimetric chemosensor capable of detecting Ni2+ ion.
Keywords: Coumarin; Colorimetric sensor; Ni2+ ion;

Two novel five-fold interpenetrating diamondlike 3D coordination polymers, namely [M(bpg)(bdc)·2H2O] (M = Zn(II), Cd(II)) have been synthesized by the hydrothermal reactions between M(NO3)2·6H2O(M = Zn(II), Cd(II)), meso-α,β-bi(4-pyridyl) glycol (bpg) and 1,4-benzenedicarboxylic acid (H2bdc). The two compounds were characterized by X-ray single crystal diffraction, infrared spectroscopy, elemental analysis, thermogravimetric analysis, and their fluorescence properties were also investigated.Two Five-fold interpenetrating diamondlike 3D MOFs have been constructed by meso-α,β-bi(4-pyridyl) glycol (bpg) and aromatic carboxylate ligands. They were characterized by X-ray single crystal diffraction, infrared spectroscopy, elemental analysis, thermo gravimetric analysis, and their fluorescence properties were also investigated.Display Omitted► The functional flexible ligand meso- α,β-bi(4-pyridyl) glycol. ► Two five-fold interpenetrating diamondlike 3D coordination polymers. ► The luminescent properties of d10 metal-organic polymers.
Keywords: Coordination polymer; Diamondoid structure; Five-fold interpenetration; Luminescent properties;

In situ hydrothermal synthesis of two novel Cd(II) coordination compounds by Guo-Jie Yin; Bao-Ming Ji; Chen-Xia Du (21-24).
Hydrothermal in-situ reactions of 4,4′-bis(3,3′-dicyano)pyridine (pydcy) with Cd(NO3)2·6H2O under the similar reaction condition but different solvent media result in two new compounds [C48H32Cd2N8O18](1) and [C17H13CdN3O5](2). Compound 1 features a new dimeric carboxylate bridged structure, while compound 2 gives a 3D framework with large hexagon channels embodied with water molecules. Topology analysis of 2 defines a type of {83} etb topology. TGA and XRPD analysis indicated that the guest water molecules in 2 can be removed to result in a nanoporous network. Both compounds exhibit intense fluorescence at room temperature, which may originate from the ligand-to-metal charge transfer (LMCT) state.Two novel Cd(II) coordination compounds based on this ligand under similar conditions but different solvent media were conveniently synthesized and characterized by X-ray crystallography.Display Omitted► Two new Cd(II) compounds are obtained by the in-situ hydrothermal reactions. ► The frameworks of the complexes are profoundly influenced by the solvent media. ► Water molecules in compound 2 can be removed to result in a nanoporous network. ► Both compounds exhibit intense fluorescence at room temperature.
Keywords: Coordination polymers; 4,4′-bis(3,3′-dicyano)pyridine; Crystal structure; Hydrothermal synthesis;

Photoluminescences and 1D chain-like structures with dinuclear lanthanide(III) units featuring bipyridine-tetracarboxylate by Wu Mingyan; Jiang Feilong; Zhou Youfu; Feng Rui; Chen Lian; Hong Maochun (25-28).
Four isostructural lanthanide(III) complexes, [Ln2(HL)2(H2O)4]n·2nH2O (H4L = 3,3′,6,6′-tetracarboxyl-2,2′-bipyridine) (Sm (1), Eu (2), Gd (3), Tb (4)), have been synthesized under the hydrothermal condition and characterized by single-crystal X-ray diffractions, powder X-ray diffractions (PXRD), thermal analyses (TGA) and elemental analyses (EA). These four complexes all exhibit 1D chain-like structures containing di-nuclear lanthanide(III) units, which are further linked by hydrogen bonding into 3D supramolecules. To further investigate the properties of the above complexes, the photoluminescent properties of 2 and 4 are also discussed.Four lanthanide(III) complexes all exhibit 1D chain-like structures containing di-nuclear lanthanide(III) units, which are further linked by hydrogen bonding into 3D supramolecules. To further investigate the properties of the above complexes, the photoluminescent properties of 2 and 4 are also discussed.Display Omitted► The four lanthanide(III) complexes all contain di-nuclear lanthanide(III) units. ► The photoluminescent properties of 2 and 4 are discussed in detail. ► The results show the ligand HL3− can effectively transfer energy to lanthanide ions.
Keywords: Lanthanide(III); 3,3′,6,6′-tetracarboxyl-2,2′-bipyridine; Crystal structure; Luminescence;

New Pb(II)-selective membrane electrode based on a new Schiff base complex by Xiao-Ju Yuan; Rui-Ying Wang; Chun-Bo Mao; Lian Wu; Cai-Qing Chu; Rui Yao; Zhi-Yang Gao; Ben-Lai Wu; Hong-Yun Zhang (29-32).
Schiff base complex [Co(L)2](ClO4)·(C3H6O)·(H2O) (1) was synthesized and structurally determined [L = 2-((E)-(3-aminopyridin-4-ylimino)methyl)-phenol and C3H6O = acetone]. With 1 as the ionophore a new Pb(II)-selective membrane electrode was exploited. The electrode exhibits Nernstian response to Pb(II) over a wide concentration range (1.0 × 10− 5 to 1.0 × 10− 2  M), with a slope of 23.9 mV/dec, a fast response time (t 95%  = 10 s), and a lower detection limit of 4.6 × 10− 6  M. It has acceptable selectivity for Pb(II) over a wide variety of other metal ions in a wide pH range of 4–13, showing practical detection for Pb(II).A new Pb(II)-selective membrane electrode with mononuclear Schiff base complex [Co(L)2](ClO4)·(C3H6O)·(H2O) (1) [L = 2-((E)-(3-aminopyridin-4-ylimino)methyl)-phenol and C3H6O = acetone] as the ionophore was synthesized and investigated.Display Omitted► Ionophore of Schiff base complex. ► Crystal structure of mononuclear Co(II) complex. ► Pb(II)-selective membrane electrode. ► Potentiometric sensor.
Keywords: Ionophore of Schiff base complex; Crystal structure; Pb(II)-selective membrane electrode; Potentiometric sensor;

A metal–organic framework of [Co(II)(1,4-benzenedicarboxylate)2(pyridine)2(water)2] has been synthesized and characterized by IR spectra, TGA and single crystal X-ray diffraction analysis. Discrete cyclic hexameric water clusters through carboxylate oxygens and pyridine molecules are trapped inside a two-dimensional coordination channel.Discrete cyclic hexameric water clusters and pyridine molecules are trapped inside a two-dimensional coordination polymer. Thermal analysis shows that the oxygen atom of water is strongly incorporated as a part of this cluster.Display Omitted► A Co(II) coordinated polymer, has been synthesized under hydrothermal condition. ► The 3D supramolecular structure is formed by π–π interaction and H―O―H hydrogen bondings. ► The water cluster plays important role to make 3D supramolecular. ► Thermal analysis shows that the oxygen atom of water is strongly incorporated as a part of this cluster.
Keywords: Co(II) complex; 3D supramolecular structure; Water cluster; TGA;

Synthesis, characterization and properties of a tri(N-heterocyclic carbene) palladium(II) complex by Tressia A.P. Paulose; Shih-Chang Wu; J. Wilson Quail; Stephen R. Foley (37-39).
The synthesis and characterization of an air and moisture stable tri(N-heterocyclic carbene) (triNHC) palladium(II) complex are described. The triNHC ligand is unique in that it is designed to allow for meridional chelation wherein all three carbene moieties can coordinate in the same plane to the metal center, unlike all prior triNHC ligands which exhibit pseudo-facial or tripodal coordination modes.A chelating tri(N-heterocyclic carbene) ligand is described wherein all three NHC moieties coordinate meridionally in a chelating fashion thus resulting in a triNHC ligand that is ideal for square planar geometries.Display Omitted► Synthesis of a tri(N-heterocyclic carbene) palladium(II) complex. ► First example of a triNHC ligand where all three NHC moieties coordinate meridionally. ► [(triNHC)PdCl]Cl exhibits exceptional thermal stability.
Keywords: N-heterocyclic carbene; Palladium; TriNHC; Chelating NHC ligands;

The synthesis, structural and solution properties of a novel cobalt aquo-pyridine complex [Co(nta)(py)(H2O)] (nta = nitrilotriacetate) are reported. Characterisation of the new complex was performed by 1H NMR, FTIR and single crystal X-ray diffraction. Substitution kinetics with NCS ions over a large pH range indicates that pyridine induces a small cis effect.A novel cobalt(III) complex with nta (nta = nitrilotriacetate), [Co(nta)(py)(H2O)], has been synthesized, structurally characterized and the aqueous substitution kinetics with thiocyanate ions have been evaluated.Display Omitted► A novel cobalt(III) monomeric complex with nitrilotriacetate was synthesized. ► The introduction of py as base, decrease the formation of unwanted byproducts. ► Substitution kinetics illustrates low cis effect of py. ► The title complex can easily be used for further synthesis.
Keywords: Cobalt; Nitrilotriacetate (nta); Pyridine; Crystal structure; Substitution kinetics;

Novel DNA photocleavage properties of [Cr(NN)3]3+ complexes by Judith Toneatto; Guadalupe Lorenzatti; Ana M. Cabanillas; Gerardo A. Argüello (43-46).
The aim of this study was to investigate the ability of chromium(III) tris-diimine complexes, [Cr(NN)3]3+, to induce DNA photodamage and to examine its capability to impair the survival of irradiated bacteria with the purpose of using these compounds as photocleavage reagents.[Cr(NN)3]3+ complexes, where NN stands for the ligands: phen (1,10-phenanthroline), 5-Mephen, 4,7-diMephen, 3,4,7,8-tetraMephen, 5-Phphen and 5-Clphen were used for this purpose. Their properties of DNA photocleavage were investigated by electrophoretic studies and assays of the photosensitization of transformed bacteria. The results clearly indicate that [Cr(NN)3]3+ complexes promote the photocleavage of plasmid DNA with varied degrees of efficiency after 12 h of irradiation. The combination of DNA, [Cr(NN)3]3+ and light proved to be required to induce the breakdown of DNA. Irradiated plasmid DNA-[Cr(NN)3]3+ association is also capable of impairing the transforming capacity of bacteria. These results provide evidence which confirms the responsibility and essential role of the excited state of [Cr(NN)3]3+ for inducing damage. Moreover, assays of the photosensitization of transformed bacterial suspensions suggest that Escherichia coli may be photoinactivated by irradiation in the presence of [Cr(NN)3]3+ complexes.[Cr(NN)3]3+ complexes are able to cause plasmid DNA photocleavage and cellular photoinactivation.Display Omitted► [Cr(NN)3]3+ complexes promote the photocleavage of plasmid DNA with varied degrees of efficiency after 12 h of irradiation. ► Irradiated plasmid DNA-[Cr(NN)3]3+ association is also capable of impairing the transforming capacity of bacteria. ► Photosensitization of transformed bacterial suggest that E. coli is inactivated by irradiation in presence of [Cr(NN)3]3+.
Keywords: Chromium(III) complexes; Photosensitization; DNA photocleavage; Bacterial transformation; Bacterial growth photoinhibition;

An unprecedented 2D → 3D polythreaded metal-lomefloxacin complex assembled from sidearm-containing 2D motifs by Shi-Wei Yan; Hai-Yan Chen; Dong-Rong Xiao; Jiang-Hong He; Guang-Ju Zhang; Dian-Zhen Sun; Ruo Yuan; En-Bo Wang (47-51).
An unprecedented entangled metal-lomefloxacin complex, [Cd(1,4-bdc)(lomeH)]·1.25H2O (1) (1,4-bdc = 1,4-benzendicarboxylate, lomeH = lomefloxacin), displays a (2D → 3D) polythreaded framework self-assembled from 2D (4,4) nets with dangling lomeH ligands, which, not only represents the first and only example of polythreaded metal-quinolone complex, but also represents the first entangled coordination polymer constructed from mixed lomefloxacin and dicarboxylate ligands. Furthermore, when the strong hydrogen bonds between layers are taken into account, the resulting net of 1 becomes a binodal (3,10)-connected 3D self-penetrating network with an unprecedented (4.52)2(46.520.617.82) topology, which represents the first binodal (3,10)-connected self-penetrating network observed in coordination polymers.The first polythreaded metal-quinolone complex, assembled from 2D (4,4) nets with dangling lomefloxacin ligands, is reported, which, not only represents the first entangled metal-lomefloxacin complex, but also represents the first binodal (3,10)-connected self-penetrating network if H-bonds are taken into account.Display Omitted► Compound 1 defines an unprecedented (2D → 3D) polythreaded framework assembled from 2D (4,4) nets with dangling lomeH ligands. ► Compound 1 represents the first and only example of polythreaded metal-quinolone complex. ► Compound 1 also represents the first example of entangled metal-lomefloxacin complex. ► Compound 1 defines the first binodal (3,10)-connected self-penetrating network observed in coordination polymers if H-bonds are taken into account.
Keywords: Lomefloxacin; Metal-quinolone complex; Polythreaded network;

Catalytic efficiency of a novel complex of oxoperoxo molybdenum(VI): Synthesis, X-ray structure and alkane oxidation by Mojtaba Bagherzadeh; Mojtaba Amini; Arkady Ellern; L. Keith Woo (52-55).
A new mononuclear oxo–peroxo complex of molybdenum(VI) of the formula [MoO(O2)(phox)2] (where phox = 2-(2′-hydroxyphenyl)oxazoline) has been synthesized and characterized by X-ray structure analysis, elemental analysis, infrared, UV–visible and 1H, 13C NMR spectroscopy. A monoclinic space group P−1 was determined by X-ray crystallography from single-crystal data of this complex. Complex functions as facile alkane oxidation catalyst with hydrogen peroxide as terminal oxidant at room temperature. The catalyst shows very much efficient reactivity in the oxidation reactions giving high yield, turnover number (TON) and selectivity.A new oxo–peroxo molybdenum(VI) complex [MoO(O2)(phox)2] was synthesized and characterized. The complex efficiently catalyzes the selective oxidation of alkanes to the corresponding aldehydes/ketones and alcohols with excellent selectivity using H2O2 as an oxidant.Display Omitted► A oxo–peroxo molybdenum(VI) complex is applied in oxidation of alkanes. ► Hydrogen peroxide (H2O2) as oxidant. ► Excellent yield, high TONs and selectivity have been achieved.
Keywords: Oxo–peroxo complex; Molybdenum; Alkane; Oxidation;

Two new tetradentate ligands Timpy (1,2-bis((E)-(2-phenyl-2-(pyridine-2-yl)hydrozono)methyl)benzene) and Gimpy ((1Z,2Z)-1,2-bis(2-phenyl-2-(pyridine-2-yl)hydrozono)ethane) were synthesized and characterized. Mononuclear complexes [Cu(Timpy)(ClO4)](ClO4) (1) and [Cu(Gimpy)](ClO4)2 (2) were synthesized and characterized by IR, UV–visible and conductivity measurements. The molecular structure of [Cu(Timpy)(ClO4)](ClO4) (1) was determined by single crystal X-ray diffraction and structural index parameter (τ  = 0.4725) supported distorted square planar geometry at the metal centre. Electrochemical studies for 1 and 2 were investigated. Two-fold applications of these complexes were examined. First, self-activated DNA cleavage activity of complexes 1 and 2 and mechanism of nuclease activity. Second, the complexes were utilized as fluorescence probe for the detection of nitric oxide in solution.Mononuclear copper(II) complexes [Cu(Timpy)(ClO4)](ClO4) (1) and [Cu(Gimpy)](ClO4)2 (2) derived from tetradentate ligands Timpy and Gimpy. Two-fold applications of these complexes will be described. First, these complexes were efficient in cleaving DNA in self-activated pathway and enhancement of nuclease activity was observed in presence of oxidizing or reducing agent. Second, the complexes were utilized as fluorescence probe for the detection of nitric oxide.Display Omitted► Copper complexes derived from tetradentate ligands were synthesized. ► Ligands and complexes were characterized by spectroscopic studies. ► Molecular structure of representative complex was determined by X-ray crystallography. ► Nuclease activity happened via self-activation. ► Nitric oxide detection in solution by fluorescence measurement.
Keywords: Copper complexes; Crystal structure; Electrochemistry; Nuclease activity; Self-activation; NO reactivity;

Compound {(EMIM)2[Zn74-O)2(1,4-ndc)6]}n (1) (EMIM = 1-ethyl-3-methylimidazolium and 1,4-ndc = 1,4-naphthalenedicarboxylate) has been synthesized by using the mixed ionic liquids of 1-ethyl-3-methylimidazolium tetrafluoroborate and 1-ethyl-3-methylimidazolium l-lactate as solvent. Compound 1 has a 3D anionic framework with bcu-(424·64) topology based on a unique heptanuclear [Zn74-O)(μ2-COO)10] cluster as secondary building unit. The imidazolium cation [EMIM]+ of the ionic liquid acting as extra framework charge-balancing species occupies the channels of the 3D anionic framework. The roles of the ionic liquid in ionothermal synthesis and crystallization of compound 1 are briefly discussed. The thermal and photoluminescent properties of compound 1 have also been investigated.{(EMIM)2[Zn74-O)2(1,4-ndc)6]}n (1) (EMIM = 1-ethyl-3-methylimidazolium and 1,4-ndc = 1,4-naphthalenedicarboxylate) has been synthesized under ionothermal reaction. Compound 1 has a 3D anionic framework with bcu-(424·64) topology based on heptanuclear [Zn74-O)(μ2-COO)10] cluster. The thermal and photoluminescent properties of 1 have also been investigated.Display Omitted► Ionothermal synthesis. ► Zinc(II)-carboxylate cluster compound. ► Heptanuclear zinc cluster. ► 3D anionic framework with bcu-(424·64) topology.
Keywords: Ionothermal synthesis; Topology; Heptanuclear zinc cluster; Crystal structure;

Luminescent mononuclear copper(I) heteroleptic complexes with 6-cyano-2,2′-bipyridine by Jing-Lin Chen; Xing-Fu Cao; Wei Gu; Bo-Tao Su; Feng Zhang; He-Rui Wen; Ruijin Hong (65-68).
A new series of luminescent mononuclear Cu(I) heteroleptic complexes of 6-cyano-2,2′-bipyridine (cbpy), [Cu(cbpy)(PPh3)X] (X = I (1); Br (2)) and [Cu(cbpy)(PPh3)2](ClO4) (3), has been synthesized and characterized. It is revealed that phosphine in place of halide results in lengthening of the Cu―P bond from 2.21 Å of 1 and 2.19 Å of 2 to 2.27 Å of 3. Complexes 13 display the weak low-energy absorption bands in the 350–600 nm region in dichloromethane, which are assigned to the Cu(I) to cbpy metal-to-ligand charge-transfer (MLCT) transitions, probably mixed with some halide-to-ligand charge-transfer (XLCT) character for 1 and 2. Complexes 13 show the solid-state emissions at ambient temperature, varying with the second auxiliary ligand coordinated to the {Cu(cbpy)(PPh3)} motif, which most likely originate from the MLCT excited states, perhaps involving some XLCT character for 1 and 2.A new series of three luminescent Cu(I) heteroleptic complexes of 6-cyano-2,2′-bipyridine (cbpy) has been synthesized and characterized. It is demonstrated that the second auxiliary ligand introduced into the {Cu(cbpy)(PPh3)} motif has a significant impact on the luminescence properties of Cu(I) cbpy complexes.Display Omitted► A new series of Cu(I) complexes [Cu(cbpy)(PPh3)L]0/+ (L = I (1); Br (2); PPh3 (3)). ► Complexes 13 are all emissive in the solid state at room temperature. ► The second auxiliary ligand has important impacts on the structures and properties.
Keywords: Copper(I); Mixed-ligand; Photoluminescence; 6-Cyano-2,2′-bipyridine;

The reactions of 2-hydroxybenzhydrazide (salicylhydrazide; Hshz) with trans-[ReOX3L2] (X = Cl (a), Br (b); L = PPh3] in acetonitrile and acetone were studied. With a in acetonitrile, the rhenium(III) complex [ReCl2(shz)(NCCH3)L2] (1), with shz coordinated as a monodentate diazenide, was isolated. However, with b in acetonitrile, the oxorhenium(V) dimer (μ-shd) [ReOBr(OPPh3)]2 (2) was formed. The bridging ligand shd4− was formed by the condensation of two shz ligands, with the elimination of hydrazine. In acetone, the reaction of Hshz with a produced [ReOCl2(sha)L] (3), in which the bidentate Schiff base ligand sha was formed by the condensation of shz with acetone. The spectral and X-ray crystallographic characterization of complexes 13 are reported.The reaction of trans-[ReOBr3(PPh3)2] with salicylhydrazide (Hshz) in acetonitrile forms the ligand-bridged dimer (μ-shd)[ReOBr(OPPh3)]2.Display Omitted► Oxorhenium(V) diazenide complex. ► Ligand-bridged dimer of oxorhenium(V). ► Coordination of a neutral ketonic oxygen to rhenium(V). ► Condensation of benzhydrazide.
Keywords: Rhenium (III)/(V); Salicylhydrazide; Ligand-bridged dimer;

The first member of a second generation family of ligands derived from metal-ion assisted reactivity of di-2,6-(2-pyridylcarbonyl)pyridine: Synthesis and characterization of a MnII/III 4 rhombus by Theocharis C. Stamatatos; Rosa Adam; Catherine P. Raptopoulou; Vassilis Psycharis; Rafael Ballesteros; Belén Abarca; Spyros P. Perlepes; Athanassios K. Boudalis (73-77).
Nucleophilic attack by the carbanion CH2COCH3 at the carbonyl carbon atoms of 2,6-di-(2-pyridylcarbonyl)pyridine, pyCOpyCOpy, in the presence of Mnn+ ions under basic conditions has yielded the cationic cluster [Mn4(OH)2(L)2(H2O)2](ClO4)4 (1), where L2− is the (py)C(CH2COCH3)(O)(py)C(CH2COCH3)(O)(py) dianion. The cluster cation possesses a planar {MnII 2MnIII 23-OH)2(μ-OR)4}4+ rhombus core, resulting from two μ3-OH ions and two η12111213 bridging L2− groups from the in situ formed ligand. Complex 1 is antiferromagnetically coupled with an unusual S  = 2 ground state resulting from spin frustration effects within the triangular Mn3 subunits of the cluster.Nucleophilic attack by the carbanion CH2COCH3 at the carbonyl atoms of 2,6-di-(2-pyridylcarbonyl)-pyridine, pyCOpyCOpy, in the presence of Mn n+ ions under basic conditions has yielded the cationic cluster [Mn4(OH)2(L)2(H2O)2](ClO4)4, where L2− is the (py)C(CH2COCH3)(O)(py)C(CH2COCH3)(O)(py) dianion; the latter is the first member of a second generation family of ligands derived from pyCOpyCOpy.Display Omitted► The ligand pyCOpyCOpy undergoes a metal-assisted nucleophilic attack. ► The dianion (py)C(CH2COCH3)(O)(py)C(CH2COCH3)(O)(py) acts as a bridging group. ► The {MnII 2MnIII 2} cluster possesses a rare, planar [Mn43-OH)2(μ-OR′)4]4+ core. ► The Mn4 cluster is antiferromagnetically coupled and has an S  = 2 ground state. ► Spin frustration effects stabilize the obtained, intermediate ground state.
Keywords: Crossed-aldol reactions; 2,6-Di-(2-pyridylcarbonyl)pyridine; Ligands' transformation; Magnetic properties; Polynuclear manganese complexes; Reactivity of coordinated ligands;

Postsynthetic modification of a coordination compound with a paddlewheel motif via click reaction: DOSY and ESR studies by Shuangbing Han; Zhenbo Ma; Russell Hopson; Yanhu Wei; David Budil; Stefano Gulla; Brian Moulton (78-83).
Postsynthetic strategy based on organic coupling reactions has been explored for the synthesis of novel coordination complexes with larger dimensions. A discrete coordination species with a paddlewheel motif, dicopper(II) tetracarboxylate Cu2(OOC-C6H4-N3)4(quinoline)2 (SBU1), was covalently modified with methyl propiolate via “Click” reaction to generate a new coordination compound Cu2(OOC-C6H4-C2N3H-COOCH3)4·(quinoline)2 (1). The combination of single-crystal X-ray diffraction, diffusion NMR and ESR has confirmed the success of covalently modifying SBU1 and the retention of the structural integrity after the postsynthetic modification.We report on the postsynthetic modification (PSM) of a dicopper(II) coordination compound with a paddlewheel motif via Click reaction. DOSY and ESR studies have successfully confirmed the structural integrity of the coordination chromophore.Display Omitted► A dicopper (II) coordination compound with a paddlewheel motif was covalently modified via Click reaction. ► The coordination chromophore of SBU1 was retained throughout the Click reaction process. ► The combination of NMR and ESR techniques has proved to be powerful tools to characterize structures of non-single-crystalline coordination complexes.
Keywords: Postsynthetic; DOSY; ESR; Crystal; Click chemistry; Paddlewheel;

Manganese complexes with acyclic compartmental Schiff bases by F. Benetollo; V. Peruzzo; S. Tamburini; P.A. Vigato (84-87).
The end-off acyclic compartmental ligands H5-LA and H6-LB have been prepared by [2 + 1] or [3 + 1] condensation of the appropriate amounts of pyridoxal hydrochloride with 1,3-diamine-2-propanol and 3-formylsalicylic acid with tris-2-(aminoethyl)amine, respectively. The ligand H5-LA, which contains two adjacent N2O chambers, bears an endogenous hydroxo potentially bridging group and H6-LB, which contains an inner N4O3 and an outer O3O3 compartment, bears three potentially bridging phenolic groups. The complexes [Mn2(H2-LA)(CH3COO)2](Cl)·5H2O and [Mn(H3-LB)]·0.25H2O·CH3OH have been obtained by the template condensation of the appropriate amine and formyl precursors in the presence of Mn(CH3COO)2·4H2O in methanol. When recrystallized [Mn2(H2-LA)(CH3COO)2](Cl)·5H2O undergoes demetalation reaction giving rise to [Mn(H3-LA)(H2O)2](Cl)(H2O) where the octahedral manganese(III) ion is surrounded by two axial water molecules trans with respect to the equatorial plane formed by the two imine nitrogen atoms and the two phenolate oxygen atoms of the Schiff base [H3-LA]2−. The central –OH group of [H3-LA]2−does not participate in the coordination. In [Mn(H3-LB)]·0.25H2O·CH3OH the octahedral environment about the manganese(III) ion is reached by the coordination of three carboxylate and three phenolate oxygen atoms of the external O3O3 site and the three imine nitrogen atoms are protonated.New planar and tripodal acyclic end-off compartmental Mn(III) complexes derived from pyridoxal or salicylaldehyde were characterized with EA,IR, HPLC/ESI-MS and X-ray methods. In the tripodal complex the protonation of all imine nitrogen atoms addresses the coordination of the Mn(III) ion to the outer O3O3 site.Display Omitted► Template syntheses and structure of Manganese(III) acyclic complexes. ► Schiff base by reaction of pyridoxal with 1,3-diamine-2-propanol or 3-formylsalicylic acid with tris-2-(aminoethyl)amine. ► Demetalation-metalation, site migration and transmetalation processes.
Keywords: Manganese(III) complexes; Schiff bases; Compartmental ligands; Acyclic complexes;

A trinuclear silver coordination polymer from a bipyridine bis-urea macrocyclic ligand and silver triflate by Sandipan Dawn; Sahan R. Salpage; Mark D. Smith; Shiv K. Sharma; Linda S. Shimizu (88-92).
We report herein the construction of a metal organic polymeric framework from a bipyridine macrocyclic ligand and silver triflate. The ligand consists of two triazinanone protected urea groups and two bipyridine units that coordinate with the Ag atoms in crystallographically different manners. In a unit cell of the crystal there are three independent Ag atoms and two ligands that form a basket shape enclosing two of the silver atoms. Two silver atoms are 3.13 Å apart, suggesting an Ag–Ag bond interaction. We probe the characteristics of the complex by solid-state spectroscopic techniques including UV–vis, Fluorescence, IR, NMR and Raman spectroscopy. The Raman spectra suggest that a bonding interaction indeed exists between two Ag atoms and that this proximity is not merely a packing artifact. A third silver atom helps organize these boxes into an elongated polymeric chain, and ultimately these chains stack into layers with the adjacent chains to give an intriguing supramolecular structure.A trinuclear complex Ag3(C38H46N10O2)2(CF3SO3)3(CH2Cl2)3(CH3OH)0.5 was generated from the reaction of Ag(CF3SO3) and a bipyridine containing macrocyclic bis-urea (1). The structure features a basket enclosing two silver atoms at 3.13 Å distance. This argentophilic interaction is supported by Raman spectroscopy. A third silver atom organizes these baskets into a polymeric chain.Display Omitted► A trinuclear complex was generated from silver triflate and a bipyridine macrocyclic bis-urea. ► The structure features two ligands that form a basket enclosing two of the silver atoms at 3.13 Å distance. ► An argentophilic interaction is supported by Raman spectroscopy.
Keywords: Bipyridines; Argentophilic; Coordination polymers;

Cistrans isomerization in the syntheses of ruthenium cyclam complexes with nitric oxide by Robson da Silva Vidal; Fábio Gorzoni Doro; Kleber Queiroz Ferreira; Zênis Novais da Rocha; Eduardo Ernesto Castellano; Sofia Nikolaou; Elia Tfouni (93-96).
The cis to trans isomerizations during the syntheses of trans-[Ru(NO)(OH)(cyclam)](PF6)2, from cis-[RuCl2(cyclam)]Cl, and [Ru(NO)Cl(cyclam)] (PF6)2, from cis-[RuCl2(dmso)4], are reported. The novel trans-[Ru(NO)(OH)(cyclam)](PF6)2 complex was characterized by X-ray crystallography and vibrational infrared and nuclear magnetic resonance spectroscopies. The Ru–N–O bond angle (176.75º) and ν(NO) (1835 cm− 1) suggest a nitrosonium character for this hydroxo complex. The crystal and molecular structure of trans-[Ru(NO)Cl(cyclam)](ClO4)2·2 H2O is also reported. Results presented here support the cistrans isomerization observed for the first time with ruthenium cyclam complexes. Cistrans isomerization in the syntheses of [Ru(NO)L(cyclam)] from cis-[RuCl2(cyclam)]Cl after reduction and followed by addition of nitriteDisplay Omitted ► Cistrans isomerization in the syntheses of [Ru(NO)L(cyclam)] from cis complexes. ► Trans–ruthenium nitrosyl complexes with cyclam ligand synthesized from cis analogues. ► Cistrans isomerization in the syntheses of [Ru(NO)L(cyclam)] upon addition of nitrite. ► Novel trans-[Ru(NO)(OH)(cyclam)](PF6)2 complex obtained from cis-[RuCl2(cyclam)]Cl. ► Trans-[Ru(NO)Cl(cyclam)](ClO4)2 obtained from cis-[RuCl2(dmso)4]. ► Cistrans isomerizations are supported by X-ray crystallography and other techniques.
Keywords: Ruthenium; Cyclam; Nitrosyl; Nitric oxide; Cistrans isomerization; Nitrite;

The methaneseleninate and 1,10-phenanthroline were used as ligands in the synthesis of new lanthanide complexes. The photostability, emission quantum yield (q) and quantum efficiency (η) of the 5D0 emitting level of the Eu3+ ion were determined. An energy level diagram was used to establish the most relevant channels involved in the ligand-to-metal intramolecular energy transfer process. The nephelauxetic effect was investigated to assess the covalency of the ligand–metal chemical bond. The values of the experimental 4f–4f intensity parameters, suggest that this ion is in a chemical environment less polarisable than in the case of complexes with β-diketonates as ligands.The methaneseleninate was used as ligand in the synthesis of the new Eu3+ and Gd3+ complexes. The photostability study and emission quantum yield (q) were determined. The nephelauxetic effect was investigated and an energy diagram was used to establish the most important channels involved in the intramolecular energy transfer process.Display Omitted
Keywords: Lanthanides; Methaneseleninate; Luminescence; Nephelauxetic effect;

Bisdithiolene complexes based on an extended ligand with TTF and pyridine moieties by S.I.G. Dias; S. Rabaça; I.C. Santos; L.C.J. Pereira; R.T. Henriques; M. Almeida (102-105).
The synthesis and characterization of a new extended tetrathiafulvalene (TTF) dithiolene ligand substituted with alkyl pyridine groups, pyridylethylsulfanyltetrathiafulvalenedithiolene (pesdt2−), as well as the corresponding gold (III) complex [Au(pesdt)2] obtained as a tetrabutylammonium salt are described. The oxidation potential of this complex is rather low and the paramagnetic neutral complex is obtained as an electrically insulating microcrystalline powder.The synthesis and characterization of a gold bisdithiolene complex [Au(pesdt)2] based on a novel extended dithiolene ligand containing both tetrathiafulvalene and pyridyl moieties (pesdt2− = pyridylethylsulfanyltetrathiafulvalenedithiolene) are reported.Display Omitted► Synthesis of the first pyridine substituted extended dithiolene ligand with TTF moieties (pesdt2−). ► Preparation of a new monoanionic AuIII bisdithiolene (n-Bu4N) [Au(pesdt2)]. ► A new neutral gold complex [Au(pesdt2)] which is paramagnetic, but not a good electrical conductor. ► [Au(pesdt2)] presents an EPR signal centered at 2.0026 with an effective magnetic moment of ~ 1.75 μB/fu at room temperature.
Keywords: Bisdithiolene complexes; Gold; Pyridine; Tetrathiafulvalenes;

Synthesis, structure, electrical and magnetic properties of (BEDT-TTF)2[3,3′-Fe(1,2-C2B9H11)2] by Olga N. Kazheva; Grigorii G. Alexandrov; Andrey V. Kravchenko; Igor B. Sivaev; Irina D. Kosenko; Irina A. Lobanova; Marcela Kajňaková; Lev I. Buravov; Vladimir I. Bregadze; Alexander Feher; Vladimir A. Starodub; Oleg A. Dyachenko (106-108).
New radical cation salt of bis(ethylenedithio)tetrathiafulvalenium and iron bis(dicarbollide) [BEDT-TTF]2[3,3′-Fe(1,2-C2B9H11)2] (1) has been synthesized. The crystal structure of 1 has been determined by single-crystal X-ray diffraction method found to be isostructural to the known Co and Cr analogues. The electric conductivity measurement in the range of 110 ÷ 296 К shows that 1 is semiconductor with the room temperature conductivity σ293  = 1.5 × 10−2  Ω−1  cm−1, that is higher than in the Cr analogue and lower than in the Co analogue. The measurement of magnetic susceptibility in the range of 2 ÷ 300 K revealed that 1 is paramagnetic with the absence of significant interactions between the organic radical cations and the paramagnetic anions.Radical cation salt of bis-(ethylenedithio)tetrathiafulvalenium and iron bis(dicarbollide) (BEDT-TTF)2[3,3′-Fe(1,2-C2B9H11)2] has been synthesized. Its crystal structure has been determined by single-crystal X-ray diffraction method. Electric and magnetic properties of the radical cation salt were studied. The structure–property relationships in the (BEDT-TTF)2[3,3′-M(1,2-C2B9H11)2] series (M = Cr, Fe, Co) were discussed.Display Omitted► New radical cation salt of bis(ethylenedithio)tetrathiafulvalenium and iron bis(dicarbollide) has been synthesized. ► The crystal structure of (BEDT-TTF)2[3,3′-Fe(1,2-C2B9H11)2] has been determined by single-crystal X-ray diffraction method. ► Electric and magnetic properties of (BEDT-TTF)2[3,3′-Fe(1,2-C2B9H11)2] were studied. ► The structure–property relationships in the (BEDT-TTF)2[3,3′-M(1,2-C2B9H11)2] series (M = Cr, Fe, Co) were discussed.
Keywords: Iron Bis(dicarbollide); Bis(ethylenedithio)tetrathiafulvalene; Crystal structure; Electric conductivity; Magnetic susceptibility;

The reactions of equimolar amounts of CuX (X = Br, I), triphenylphosphane and (−)-nicotine yield intensively blue emitting substances. Single crystal X-ray diffraction revealed an aggregation to dimeric Cu2X2(PPh3)2[(−)-nicotine]2. Contrary to the majority of analogue complexes of the type [Cu2X2(PPh3)2(s-py)2] (s-py = substituted pyridine), the nicotine complex does not show a considerable temperature dependence of the emission wavelength. In addition, the crystal structure of the intermediate [Cu2Br2(PPh3)2(MeCN)2] × 2MeCN is presented.The reaction of equimolar amounts of CuX (X = Br, I), triphenylphosphane and (−)-nicotine yields the dimeric complexes Cu2X2(PPh3)2[(−)-nicotine]2 featuring intense blue luminescence upon photo-excitation in the solid state. Contrary to the majority of analogue complexes of the type [Cu2X2(PPh3)2(s-py)2] (s-py = substituted pyridine), the nicotine complexes do not show a considerable temperature dependence of the emission wavelength. In addition, the crystal structure of the intermediate [Cu2Br2(PPh3)2(MeCN)2] × 2MeCN is presented.Display Omitted► Dimeric complexes of the type Cu2X2(PPh3)2[(−)-nicotine]2 (X = Br, I) have been synthesized and structurally characterized. ► They feature intense blue luminescence upon photo-excitation in the solid state. ► Additionally, the crystal structure of the intermediate [Cu2Br2(PPh3)2(MeCN)2] × 2MeCN is presented.
Keywords: Copper; Nicotine; Crystal structure; Luminescence; Singlet harvesting;

A matter of greasy tails: Interdigitation of alkyl chains in free and coordinated 4′-(4-dodecyloxyphenyl)-4,2′:6′,4″-terpyridines by Edwin C. Constable; Guoqi Zhang; Catherine E. Housecroft; Jennifer A. Zampese (113-116).
The syntheses and single crystal structures of 4′-(4-dodecyloxyphenyl)-4,2′:6′,4″-terpyridine, 2, and [Zn2(μ-OAc)4(2)2] are reported. Crystal packing is dominated by van der Waals interactions between fully extended alkyl chains producing lamellar structures in both compounds, and appears to be the reason for the formation of crystalline [Zn2(μ-OAc)4(2)2] rather than a one-dimensional coordination polymer as observed for related compounds.Syntheses and single crystal structures of 4'-(4-dodecyloxyphenyl)-4,2':6',4''-terpyridine, 2, and [Zn2(μ-OAc)4(2)2] are described. In the solid state, van der Waals interactions between extended alkyl chains result in lamellar structures and influence the preference for the assembly of discrete molecules of [Zn2(μ-OAc)4(2)2] rather than a one-dimensional coordination polymer.Display Omitted► Divergent 4,2′:6′,4″-terpyridine ligands with long alkyl tails. ► Controlling the assembly of mononuclear zinc(II) complexes versus 1D coordination polymers. ► van der Waals forces between extended alkyl chains control structural solid-state assembly. ► Crystal structure of [Zn2(μ-OAc)4  L2], L = 4′-(4-dodecyloxyphenyl)-4,2′:6′,4″-terpyridine.
Keywords: Zinc; 4,2′:6′,4"-terpyridine; Crystal structure; Hydrophobic tail;

Reaction of the potassium salt of the N-thiophosphorylated thiourea Et2NC(S)NHP(S)(OiPr)2 (HL) with a mixture of AgNO3 and PPh3 in aqueous EtOH/CH2Cl2 leads to the mixed-ligand silver(I) complex [Ag(PPh3)2{Et2NC(S)NP(S)(OiPr)2}] ([Ag(PPh 3 ) 2 L]). Recrystallization of [Ag(PPh 3 ) 2 L] from an acetone/n-hexane mixture leads to the decomposition of the starting complex with the formation of [Ag(PPh3){Et2NC(S)NP(S)(OiPr)2}] ([Ag(PPh 3 )L]), [Ag(PPh 3 ) 3 NCS]∙(CH 3 ) 2 C=O and Et 2 NP(S)(OiPr) 2 . The structures of [Ag(PPh 3 ) 2 L], [Ag(PPh 3 )L], [Ag(PPh 3 ) 3 NCS]∙(CH 3 ) 2 C=O and Et 2 NP(S)(OiPr) 2 were all investigated by IR, 31P{1H} and 1H NMR spectroscopy, and their compositions were established by elemental analysis. The crystal structure of the complex [Ag(PPh 3 ) 3 NCS]∙(CH 3 ) 2 C=O obtained from single crystal X-ray diffraction is presented.Reaction of the potassium salt of Et2NC(S)NHP(S)(OiPr)2 (HL) with a mixture of AgNO3 and PPh3 leads to the mixed-ligand silver(I) complex [Ag(PPh3)2{Et2NC(S)NP(S)(OiPr)2}] ([Ag(PPh 3 ) 2 L]). The recrystallization of [Ag(PPh 3 ) 2 L] from an acetone/n-hexane mixture leads to the decomposition of the starting complex with the formation of [Ag(PPh3){Et2NC(S)NP(S)(OiPr)2}] ([Ag(PPh 3 )L]), [Ag(PPh 3 ) 3 NCS]∙(CH 3 ) 2 C=O and Et2NP(S)(OiPr)2.Display Omitted► We synthesized the Ag(I) mixed-ligand complex with N-thiophosphoryl thiourea and PPh3. ► The formation of [Ag(PPh3)L], [Ag(PPh3)3NCS]∙(CH3)2C=O, Et2NP(S)(OiPr)2 is observed. ► We examined the crystal structure of [Ag(PPh3)3NCS]∙(CH3)2C=O.
Keywords: Coordination chemistry; Crystal structure; Decomposition; N-thiophosphoryl thiourea; Silver(I);

Hydrothermal reaction of lanthanide(III) (Nd, Er and Tm) chloride with sodium salt of 4,4′-oxybis(benzoic) acid (H2oba) leads to the formation of two types of monocrystals: prismatic [Nd(Er)(Hoba)(oba)(H2O)2]·0.8H2O (1, 2) and plate-shaped [Tm2oba3(H2O)4]·1.38H2O (3) for which single-crystal X-ray measurements were performed. Isomorphous compounds 1 and 2 consist of eight-coordinated lanthanide ions bonded with oba, Hoba and aqua ligands into the 2D layers. In the structure 3 two types of Tm(III) centers are bridged by oba linkers into 2D layer architecture. Uncoordinated water molecules are located within the cavities between layers. Furthermore, the ATR-IR spectra of isolated monocrystals and thermal behaviours of the compounds are discussed.Three lanthanide (Nd, Er and Tm) coordination polymers based on the 4,4′-oxybis(benzoic) acid have been hydrothermally synthesized and characterized by ATR-IR spectroscopy, TG-FTIR analysis and single crystal X-ray diffraction analysisDisplay Omitted► The same hydrothermal conditions – different crystal structures. ► Two-dimensional lanthanide coordination polymers. ► Different coordination modes of oba ligand. ► The thermal decomposition of the polymers has been determined.
Keywords: Lanthanides; 4,4′-oxybis(benzoic) acid; Crystal structure; TG-FTIR;

Self-assembly of trigonal prismatic M6(μ–L)9 coordination cages by Adel M. Najar; Ceren Avci; Michael D. Ward (126-129).
The new ligand bis-bidentate ligand L, containing two pyrazolyl-pyridine chelating units connected to a 1,8-anthracene-diyl core via methylene spacers, reacts with Zn(II), Cd(II) and Cu(II) salts to form trigonal prismatic coordination cages [M6(μ–L)9]12+ in which a metal ion occupies each vertex and a bridging ligand spans each edge; the structure is stabilised by anions which occupy the central cavity and the gaps in the centres of the triangular faces, and also by extensive inter-ligand aromatic stacking between anthracenyl and pyrazolyl-pyridine groups.A new series of trigonal prismatic coordination cages, with a metal ion at each vertex and a bridging ligand along each edge, is described.Display Omitted► Self assembly of new coordination cages with a trigonal prismatic core structure. ► Cyclic triple helical M3L3 faces connected by bridging ligands. ► Fluorescent ligands containing anthracenyl bridging units.
Keywords: Self-assembly; Coordination cage; Crystal structure; Zinc; Copper; Cadmium;

Hydrothermal reactions of CeO2 with racemic tartaric acid (H2tar) at different temperature yielded two novel Cerium-Organic Framworks, [Ce2(tar)2(C2O4)(H2O)2] n ·4nH2O (1) and [Ce2(tar)2(C2O4)(H2O)4] n (2). 1 displays an unprecedented fsx-4,5-P21/c topology, which contains hydrophilic channels constructed by triple helical chains along a axis; 2 exhibits a 2D layer framework with a binodal (3,4)-connected V2O5 network. Notably, in both 1 and 2, the oxalate ligands were in situ synthesized from H2tar.Two new Cerium-Organic Frameworks with unusual topologies were obtained. One structure contains hydrophilic channels constructed by triple helical chains along a axis.Display Omitted► Two novel Ce(III) frameworks were obtained through hydrothermal reactions. ► In both 1 and 2, the oxalate ligands were in situ synthesized from H2tar. ► 1 displays an unprecedented fsx-4,5-P21/c topology. ► 1 contains hydrophilic channels constructed by triple helical chains along a axis. ► 2 exhibits a 2D layer framework with a binodal (3,4)-connected V2O5 network.
Keywords: Metal-Organic Framework; Racemic tartaric acid; Oxalate; Topology; Luminescence;

A novel photoluminescent silver(I) wire supported by 4-tert-butylbenzoate and ligand-unsupported Ag⋯Ag interactions by Fu-Jing Liu; Di Sun; Hong-Jun Hao; Rong-Bin Huang; Lan-Sun Zheng (136-139).
A novel silver(I) wire sustained by 4-tert-butylbenzoate and ligand-unsupported Ag⋯Ag interactions, [Ag3(tbb)3(NH3)2]n (1, Htbb = 4-tert-butylbenzoic acid), has been synthesized and structurally characterized. In 1, three tbb ligands bind three Ag(I) ions to form a trinuclear subunit through ligand-supported Ag⋯Ag interactions. The inversion-related subunits are further extended to an infinite 1D zigzag Ag(I) wire through the ligand-unsupported Ag⋯Ag interactions. Argentophilicity (3.0283(14)–3.0910(17) Å) plays an important role in determining the infinite silver(I) wire. The thermal stability and luminescent behavior of 1 were also discussed.A novel silver(I) wire sustained by 4-tert-butylbenzoate and ligand-unsupported Ag⋯Ag interactions has been synthesized and structurally characterized. Argentophilicity plays an important role in determining the infinite silver(I) wire.Display Omitted► A novel 1D silver(I) wire was synthesized and characterized. ► The structure of this complex was confirmed by X-ray crystallography. ► The silver(I) wire was sustained by ligand-supported and -unsupported Ag⋯Ag interactions.
Keywords: Silver(I) wire; 4-tert-butylbenzoic acid; Ag⋯Ag interaction; Crystal structure;

Topological and luminescent properties of two coordination polymers constructed from 3-pyridinepropionic acid by Youfu Zhou; Wentao Xu; Mingyan Wu; Anjian Lan; Linjie Zhang; Rui Feng; Feilong Jiang; Maochun Hong (140-145).
Two coordination polymers, [Zn(PPA)2(H2O)2]n (1) and [Cd(PPA)2]n (2) (HPPA = 3-pyridinepropionic acid) have been hydrothermally synthesized. Both of 1 and 2 crystallize in P-1 space group. Zn(II) centers in 1 are extended by PPA ligands to form the 1D chains, which are consolidated by hydrogen bonding to construct a 3D supramolecular network. The structure of 2 represents a rare binodal (3,6)-connected 2D layer with kgd topology. The luminescent properties of 1 and 2 in the solid state are discussed.Two coordination polymers, [Zn(PPA)2(H2O)2]n (1) and [Cd(PPA)2]n (2) (HPPA = 3-pyridinepropionic acid) have been hydrothermally synthesized. Compound 1 owns 1D chain structure, while the structure of 2 represents a rare binodal (3,6)-connected 2D layer with kgd topology. The luminescent properties of 1 and 2 in the solid state are consequently different.Display Omitted► Two polymers of seldom-adopted 3-pyridinepropionate (PPA) were obtained. ► [Cd(PPA)2]n (2) with a rare kgd topology is first structurally characterized. ► [Zn(PPA)2(H2O)2]n (1) and 2 demonstrate a route to enhanced luminescence.
Keywords: Zinc; Cadmium; 3-pyridinepropionic acid; Photoluminescence; Topology;

Synthesis and structural characterization of five copper(I) complexes of [2,3-f]-pyrazino-[1,10]phenanthroline-2,3-dicarbonitrile and triphenylphosphine by Ye-Lan Xiao; Qiong-Hua Jin; Yu-Heng Deng; Zhong-Feng Li; Wei Yang; Man-Hua Wu; Cun-Lin Zhang (146-150).
Five new copper(I) complexes containing PPh3 and C16H6N6, [Cu(PPh3)(C16H6N6)Cl]·H2O (1), [Cu(PPh3)(C16H6N6)Br]·CH3CN (2), [Cu(PPh3)(C16H6N6)I]·CH3CN (3), [Cu(PPh3)(C16H6N6)(CN)]·0.5 CH2Cl2 (4) and Cu(PPh3)(C16H6N6)(SCN) (5) {PPh3 = triphenylphosphine, C16H6N6 = [2,3-f]-pyrazino-[1,10] phenanthroline-2,3-dicarbonitrile} have been synthesized for the first time. These complexes are obtained by the reactions of CuX (X = Cl, Br, I, CN, SCN) with the bidentate ligand C16H6N6 and the monodentate ligand PPh3 in the molar ratio of 1:1:1 in the mixed solvent of CH2Cl2 and CH3CN(5 ml/5 ml). They are characterized by X-ray crystallography, luminescence, IR, 1H NMR and 31P NMR. In solid state the complexes 15 are mononuclear with similar structures, but in solution they have different structures according to their different 1H NMR signals. All the complexes exhibit intense luminescence in solid state at room temperature.Five copper(I) complexes containing PPh3 and C16H6N6, {PPh3 = triphenylphophine, C16H6N6 = [2,3-f]-pyrazino-[1,10] phenanthroline-2,3-dicarbonitrile} have been synthesized for the first time. 1–5 are characterized by X-ray crystallography, luminescence, 1H and 31P NMR. 1–5 in the solid state exhibit intense luminescence at room temperature.Display Omitted► Five Copper (I) complexes of [2,3-f]-pyrazino-1,10-phenanthroline-2,3-dicarbonitrile are reported. ► The coordination chemistry of C16H6N6 is interesting. ► 1–5 exhibit intense luminescence peaks around 450 nm in solid state. ► The intensity of the emission peaks is increased because of the ligand C16H6N6. ► The 1H and 31P NMR spectra of 1–5 are dependent on the counter anion.
Keywords: Copper(I); Crystal structure; Luminescence; Triphenylphosphine; [2,3-f]-Pyrazino-[1,10]phenanthroline-2,3-dicarbonitrile;

The first Co(III)/Co(III) ionic complex with hydrazone and azide ligands, [Co(L)2]+[Co(L)(N3)3]∙ CH3OH, was structurally and electrochemically characterized, where HL =  N′-[(1E)-1-pyridin-2-ylethylidene]-2-furohydrazide. In the cation [Co(L)2]+ two furanhydrazone, each of them with the three donor atoms, constitute a meridional arrangement around the cobalt atom. The coordination polyhedra are a CoO2N4 distorted octahedron for cation and a CoON5 distorted octahedron for anion. Cyclic voltammetric experiments of the [Co(L)2]+[Co(L)(N3)3] in DMSO reveal reduction of the L ligand at − 1.56 V and two reduction potentials at − 0.81 and − 1.28 V for two different Co(III).The first Co(III)/Co(III) ionic complex with hydrazone and azide ligands, [Co(L)]+[Co(L)(N)]∙ CH3OH, was structurally and electrochemically characterized, where HL =  N′-[(1E)-1-pyridin-2-ylethylidene]-2-furohydrazide.Display Omitted▶ The first Co(III)/Co(III) ionic complex with hydrazone and azide ligands is reported. ▶ In the cation two furanhydrazone constitute a meridional arrangement around the cobalt atom. ▶ Voltammetric study of the complex show the reduction of ligand and two Co(III).
Keywords: Cobalt ionic complex; Hydrazone Schiff base; Azide; Crystal structure; Cyclic voltammetry;

By the hydrothermal reactions of Nd2O3 with 2,2′-binicotinic acid (H2Bn) in the absence and presence of 4,4′-bipyridine(4,4′-bpy), two complexes, [Nd2(Bn)3(H2O)2]·4.5H2O (1) and [Nd2(Bn)3(H2O)2]·2H2O(4,4′-bpy) (2) were synthesized, of which the 4,4′-bpy-free 1 shows only the emissions based on Bn2 − within 300–500 nm, but the 4,4′-bpy-containing 2 shows also a band centered at 640 nm attributable to the exciplex [(4,4′-bpy)·Bn2 −]* coupled through π–π interaction.The packing and luminescence of 2, in comparison with those of 1, reveal a novel supramolecular effect of Bpy on the 2D neodymium (III) coordination polymer.Display Omitted► The synthetic strategy and structures of 1 and 2. ► Water aggregations in 1 (left) and 2 (right). ► The solid emission spectra of 1 and 2 along with that of ligand.
Keywords: Neodymium(III); Binicotinic acid; Coordination polymer; Photoluminescence;

A novel lanthanide metal-organic framework (MOF), (bpy) [Eu (ip)1.5(H2O)4] (bpy = 4,4′-bipyridine, ip = isophthalate) (1) has been synthesized via hydrothermal method. Single-crystal X-ray analysis reveals that the three-dimensional (3D) network is formed by one-dimensional (1D) chains through hydrogen bonds. The channel regions of the framework are host to neutral 4,4′-bipyridine molecules which serve as guest-templates. These 4,4′-bipyridine molecules do not coordinate to the metal centers but rather show hydrogen bond participation with metal-bound water molecules. The emission spectra show that 1 emits intense sharp red light when it is excited by different wavelength light of the absorption band.A novel lanthanide metal-organic framework (MOF) has been synthesized via hydrothermal method. Single-crystal X-ray analysis reveals that the three-dimensional (3D) network is formed by one-dimensional (1D) chains through hydrogen bonds. The channel regions of the framework are host to neutral 4,4′-bipyridine molecules which serve as guest-templates. The emission spectra show that 1 emits intense sharp red light.Display Omitted► A novel lanthanide metal-organic framework (MOF) has been synthesized via hydrothermal method. ► The three-dimensional (3D) network is formed by one-dimensional (1D) chains through hydrogen bonds. ► The channel regions of the framework are host to neutral 4,4′-bipyridine molecules which serve as guest-templates. ► The 4,4′-bipyridine molecules show hydrogen bond participation with metal-bound water molecules. ► The framework emits intense sharp red light.
Keywords: Lanthanide; Metal-organic framework; Templates; Isophthalate; 4,4′-Bipyridine; Luminescence;

The complexes, [PdCl2(L)] (12) (L  =  N-{2-(aryltelluro)ethyl}morpholine/piperidine) have been synthesized and characterized by multi-nuclei NMR and single crystal X-ray crystallography. They on reaction with aryl chloride/bromide and morpholine/piperidine give ~ 5 nm size nano-particles of PdTe. The 0.005 mol% of 2 is suitable for Heck coupling (conversion up to 93%).The complexes, [PdCl2(L)] (12) (L =  N-{2-(aryltelluro)ethyl}morpholine/piperidine) synthesized and characterized by multi-nuclei NMR and single crystal X-ray crystallography give ~ 5 nm size nano-particles of PdTe when reacted with aryl chloride/bromide and morpholine/piperidine. The 0.005 mol% of 2 is suitable for Heck coupling (conversion up to 93%).Display Omitted► Pd(II)-N-{2-(aryltelluro)ethyl}morpholine/piperidine complexes (1/2) synthesized. ► Their single crystal structures determined. ► PdTe NP’s (~ 5 nm) formed in catalyzing C-N coupling with 1/2. ► Conversion was up to 93% in Heck coupling catalyzed with 0.005 mol% of 2.
Keywords: Palladium; Tellurium ligand; Synthesis; Structure; Nano-particle; Heck coupling;

Chiral Schiff base trans-N,N′-bis-(2-hydroxy-1-naphthalidehydene)-(1R,2R)-cyclohexanediamine C28H26N2O2 (H2L) and its chiral coordination polymer [Zn(H2L)Cl2]n were prepared and characterized by infrared spectroscopy, elemental analyses and single-crystal X-ray diffraction analysis. X-ray crystallography showed that the proton transfer of phenolic hydroxyl occurred in the chiral ligand and the complex. The chiral ligand demonstrates a one-dimensional helix chain. The Zn(II) ion is four-coordinated by two oxygen atoms in different ligands and two chlorine ions, forming a distorted tetrahedron geometry. The two coordinated oxygen atoms exist in different forms, one is in keto form and the other in phenol form. The metal ions are bridged by chiral ligands and construct supramolecular which displays a one-dimensional dextrorotatory helix chain. The anticancer activities of H2L and its chiral coordination polymer [Zn(H2L)Cl2]n on MDA-MB-231 breast cancer cells were also investigated. The results indicate that both of H2L and [Zn(H2L)Cl2]n can inhibit the cellular proliferation. Furthermore, [Zn(H2L)Cl2]n has higher antiproliferative activity than that of H2L. In addition, [Zn(H2L)Cl2]n can inhibit proteasomal chymotrypsin-like activity and also can induce apoptosis on human breast cancer MDA-MB-231 cells.A Chiral Schiff base (H2L) and its coordination polymer [Zn(H2L)Cl2]n were prepared and characterized by infrared spectroscopy, elemental analyses and single-crystal X-ray diffraction analysis. It was found that [Zn(H2L)Cl2]n has potential to be used as a proteasome inhibitor and anticancer agent.Display Omitted► The Chiral Schiff base and its Zn(II) coordination polymer was synthesized. ► The crystal structures of the ligand and its coordination polymer was determined. ► The coordination polymer displays one-dimensional dextrorotatory helix chain structure. ► The anticancer activities of the ligand and its coordination polymer were studied.
Keywords: Chiral Schiff base; Zn(II) coordination polymer; Crystal structure; Anticancer;

Assembly of Cu(ClO4)2·6H2O and 2-(2-pyridyl)-5-(4-pyridyl)-1,3,4-oxadiazole (L) yields a 3-D MOF {[CuL 2](ClO4)2(H2O)1/2} n (1). Single crystal X-ray diffraction indicates that 1 has a cationic open coordination framework with lvt topology, where each CuII ion is connected to four L ligands in (η3, μ2) binding mode. The lattice water and perchlorate are accommodated in the 3-D host microporous framework with two types of 1-D channels along different directions. The unusual anion-exchange property is observed for 1, showing the exclusive anion-exchange selectivity with respect to benzoate in an irreversible way.A 3-D metal–organic framework has been constructed from 2-(2-pyridyl)-5-(4-pyridyl)-1,3,4-oxadiazole and CuII perchlorate, which exhibits the exclusive anion-exchange property toward benzoate.Display Omitted► A 3-D CuII MOF with an unsymmetric ligand 2-(2-pyridyl)-5-(4-pyridyl)-1,3,4-oxadiazole is prepared. ► The cationic coordination network has an open lvt topological framework with the inclusion of perchlorate and water. ► This MOF material shows the exclusive anion-exchange selectivity to benzoate.
Keywords: Metal–organic framework (MOF); 2-(2-Pyridyl)-5-(4-pyridyl)-1,3,4-oxadiazole; lvt Network topology; Anion-exchange property; Benzoate;

A bezoimidazole-based highly selective and low-background fluorescent sensor for Zn2 + by Xiaoqing Wang; Zhipeng Liu; Fang Qian; Weijiang He (176-179).
In this article, a new benzoimidazole based Zn2 + fluorescence sensor DABI has been prepared. The sensor displays a rapid and a linear response to Zn2 + with a red-shifted 100-fold turn-on signal from the dark background. The presence of other metal ions especially Cd2 + does not interfere with its Zn2 + response. Molecular modeling study suggests that the Zn2 +-induced red shift of emission and fluorescence turn-on of DABI could be correlated to the coplanation of two aryl planes of 2-aryl substituted benzoimidazole.A new benzoimidazole based Zn2 + fluorescence sensor DABI has been prepared and the sensor displays a rapid and a linear response to Zn2 + with a 100-fold turn-on signal from the dark background. The presence of other metal ions especially Cd2 + does not interfere with its Zn2 + response.Display Omitted► DABI displays a Zn2+-induced 100-fold turn-on signal from the dark background. ► DABI shows high Zn2+ selectivity in CH3CN solution. ► The Zn2+ sensing behavior of DABI was explained well via molecular modeling study.
Keywords: Benzoimidazole; Zn2 + fluorescence sensor; Dark background;

Solvent-induced conformational isomerism of a flexible fluorinated bis(imidazole) ligand on the self-assembly of 1-D and 2-D CuII coordination polymers by Sheng-Chun Chen; Zhi-Hui Zhang; Huan Xu; Hai-Bo Gao; Rui-Rui Qin; Qun Chen; Ming-Yang He; Miao Du (180-184).
Two distinct coordination polymers [Cu(Fbix)2(NO3)2] n (1) and {[Cu(Fbix)2(NO3)2]·6H2O} n (2) have been prepared from the reactions of CuII nitrate with a flexible fluorinated ligand 2,3,5,6-tetrafluoro-1,4-bis(imidazol-1-yl-methyl)benzene (Fbix) under different solvents. Single crystal X-ray diffraction reveals that 1 displays a 1-D double-chain structure containing the Fbix with gauche conformation whereas 2 has a 2-D rhombic grid network containing the Fbix with anti conformation. Their spectroscopic, thermal, and fluorescence properties have also been investigated.Two new CuII coordination polymers [Cu(Fbix)2(NO3)2] n (1) and {[Cu(Fbix)2(NO3)2]·6H2O} n (2) have been obtained through the solvent-regulated assembly of CuII nitrate and a flexible fluorinated ligand 2,3,5,6-tetrafluoro-1,4-bis(imidazol-1-yl-methyl)benzene (Fbix). Their significant structural discrepancy of the 1-D (for 1) and 2-D (for 2) networks results from the conformational isomerism of the Fbix ligands.Display Omitted► A novel flexible fluorinated bis(imidazole) building block is used to creat two CuII coordination polymers. ► Structural discrepancy of the 1-D and 2-D networks results from the varied conformations of the ligands. ► Thermal behavior and solid-state fluorescent emissions are available.
Keywords: Flexible tecton; Conformation isomerism; Solvent effect; Coordination polymer;

A new anion [CdBr4(C7H5O2)]3 −, where C7H5O2 = benzoate, has been isolated for the first time in the form of complex salt [Co(en)3] [CdBr4(C7H5O2)]·H2O(1). This is the first example where Cd(II) centre is coordinated by both inorganic and organic ligands and existing as discrete unit. The complex salt is characterized by spectroscopic techniques and single crystal X-ray crystallography. The formation of complex salt is also supported by DFT calculations.Complex salt [Co(en)3] [CdBr4(C7H5O2)]·H2O containing new anion [CdBr4(C7H5O2)]3 −, where C7H5O2 = benzoate, has been synthesized, characterized by physico-chemical techniques and X-ray crystallography and supported by DFT calculations. This is the first example where penta-coordinated Cd(II) metal ion is coordinated by organic (benzoate) and inorganic (bromide) ligands and existing as discrete entity.Display Omitted► Synthesis of new anion [CdBr4(C7H5O2)]3 −, where C7H5O2 = benzoate, has been presented. ► Synthesis and crystal structure of [Co(en)3][CdBr4(C7H5O2)]·H2O has been described. ► Presents first example where Cd(II) centre containing both benzoate and bromide ligands exists as discrete unit.
Keywords: New anion; Benzoatotetrabromocadmate(II); DFT calculations; X-ray crystallography;

Mg(II) and Zn(II) tetrathiafulvalene bicarboxylates with hydrogen-bond-assembled band-like supramolecular structures by Qiong-Hua Han; Zheng Shi; Ming-Yan Shao; Xin-Yu Li; Qin-Yu Zhu; Jie Dai (190-193).
Two coordination compounds, [Mg(HL)(phen)(H2O)3]·HL·phen (1) and [Zn2L2(phen)2(H2O)2] (2), with dimethylthio-tetrathiafulvalene-bicarboxylate ligand (L) have been prepared by temperature controlled solvothermal reaction. Crystal structure analysis revealed that compound 1 is a mononuclear octahedral complex with co-crystallized free ligands, while compound 2 is a dimer with two square pyramidal metal centers. Both the compounds show a 1-D band-like supramolecular structure assembled by hydrogen bonds. The hydrophilic carboxylate groups and water molecules are gathered at the centerline of the band, and the TTF moieties and phen molecules are arranged at the two sides. The molecules are further contacted through short S⋅⋅⋅S interaction forming a 2-D net. These metal-TTF-bicarboxylates are redox-active and can undergo two steps oxidization in solid state.Two transition metal complexes with dimethylthio-tetrathiafulvalene-bicarboxylate ligand are prepared by solvothermal reaction. Crystal structures of both the compounds show a 1-D band-like supramolecular structure, in which hydrophilic carboxylate groups and water molecules lie at the centerline of the band, and the TTF moieties and phen molecules lie at the sides.Display Omitted► We prepared two metal-TTF-bicarboxylate complexes by temperature controlled solvothermal reaction. ► The compounds show band-like supramolecular structure assembled by hydrogen bonds. ► These compounds are redox-active and can undergo two steps oxidization in solid state.
Keywords: Tetrathiafulvalene; Carboxylate; Coordination compound; Crystal structure; Hydrogen bond;

Synthesis, characterization, and catalytic behavior of a PSiP pincer-type ruthenium(II) complex by Yong-Hua Li; Xue-Hua Ding; Yuan Zhang; Wen-Rui He; Wei Huang (194-197).
The synthesis and characterization of a cyclometalated ruthenium(II) complex [RuCl(PSiPCy)] containing monoanionic, tridentate coordinating PSiP-pincer ligand [κ3-(2-Cy2PC6H4)2SiMe] ([PSiPCy]) are reported. Complex 3 is one of the few examples of halogenated ruthenium(II) complexes supported by the pincer-like bis(phosphino)silyl ligand. The structure of complex 3 was unambiguously determined by multinuclear NMR and single crystal X-ray analysis. This compound has also been shown to catalyze the transfer hydrogenation of ketones to the corresponding secondary alcohols efficiently with 2-propanol as the hydrogen source instead of using molecular dihydrogen gas or hazardous reducing agents (e.g., NaBH4 and LiAlH4), and tBuOK as the base.The synthesis and characterization of a cyclometalated ruthenium(II) complex 3 containing a monoanionic, tridentate coordinating PSiP-pincer ligand are reported. Complex 3 has also been shown to catalyze the transfer hydrogenation of ketones to the corresponding secondary alcohols efficiently with 2-propanol as the hydrogen source.Display Omitted► A cyclometalated Ru(II) complex. ► One of the few examples of halogenated Ru(II) complexes supported by (cyclohexylphosphino)silyl ligand. ► Catalyst for the transfer hydrogenation of ketones to alcohols.
Keywords: Ruthenium; Silyl; Pincer; Transfer hydrogenation; Tridentate ligands;

A new 2D honeycomb-like cluster polymer built by a {Mn6Na3} cluster: Synthesis and magnetic property by Yun-En Xie; Chong-Bing Tian; Hua-Bin Zhang; Yan Peng; Xian-Qiang Li; Zhi-Hua Li; Ping Lin; Shao-Wu Du (198-201).
A new 2D polymer, {[Mn6Na36-O)(thme)4(PhCO2)6(μ-H2O)3][OH]}n (1), has been synthesized and characterized by single crystal X-ray diffraction, XRD, IR spectroscopy, thermogravimetric analysis (TGA) and magnetic measurements. Compound 1 has a 2D honeycomb-like structure constructed by heterometallic {Mn6Na3} clusters, which are linked by water molecules cross-bridged between the Na (I) ions of the adjacent clusters. Magnetic property study reveals the existence of antiferromagnetic couplings between Mn (III) ions within the {Mn6Na3} clusters.A new 2D honeycomb-like polymer based on a {Mn6Na3} cluster has been synthesized by employing mixed ligands of 1,1,1-tris(hydroxymethyl)ethane and benzoic acid under aerobic conditions at room temperature. The DC and AC magnetic properties of the title compound have also been examined.Display Omitted► A new 2D honeycomb-like cluster polymer based on a {Mn6Na3} cluster has been synthesized. ► The 2D layers are staggered in a ABCABC manner leading to a plum blossom pattern along the c axis. ► Magnetic property study reveals the existence of antiferromagnetic couplings between Mn(III) ions within the {Mn6Na3} cluster.
Keywords: H3thme; Coordination polymer; Mn (III)/Na (I) cluster; Magnetic property;

A new three-dimensional uninodal eight-connected metal–organic framework (MOF) based on pentanuclear cadmium subunits has been synthesized and characterized. To our knowledge, this is the first example of MOFs with the eight-connected 34414510 topology. The framework exhibits high thermal stability until 300 °C confirmed by thermogravimetric analysis and has a potential application as a multifunctional material with fluorescent and nonlinear optical (NLO) properties.A new three-dimensional uninodal eight-connected MOF based on pentanuclear cadmium subunits has been synthesized, which is the first example of MOFs with the 34414510 topology. The framework has a potential application as a multifunctional material with fluorescent and NLO properties.Display Omitted► A new 3D uninodal MOF based on pentanuclear cadmium subunits has been synthesized. ► It's the first example of MOFs with the eight-connected 34414510 topology. ► It has a potential application as a multifunctional material with fluorescent and NLO properties.
Keywords: Eight-connected; 34414510 topology; Multifunctional material; NLO;

A 2D silver-iodide-organic framework with both fluorescent and phosphorescent emissions by Lian Chen; Jie Ma; Qihui Chen; Rui Feng; Feilong Jiang; Maochun Hong (208-211).
Treatment of bix (1, 4-bis(imidazole-1-ylmethyl)benzene) with AgI generated [(Ag4I4)(bix)] n 1, whose crystal structure reveals a 2D organic–inorganic layer formed by novel wave-like silver(I) iodide chains with the linkers of bix ligands. The layers are arranged in parallel with the mode of {ABAB…} type showing 1D rectangular channels. In solid state, 1 exhibits multiple emission properties originating from its different natures, while optical absorption spectrum suggests that 1 might be a potential wide-gap semiconductor.A 2D organic-inorganic layer structure [(Ag4I4)(bix)] n (1) (bix=1,4-bis(imidazole-1-ylmethyl)benzene) was reported, which formed by novel wave-like silver(I) iodide chains with the linkers of ligands. The layers are arranged in parallel with the {ABAB…} mode showing 1D rectangular channels. 1 exhibits multiple emissions properties originating from its different natures.Display Omitted► A 2D organic–inorganic layer based on novel wave-like silver(I) iodide chains. ► The layers are arranged in parallel with the mode of {ABAB…} type showing 1D rectangular channels. ► Exhibiting multiple emissions properties originating from its different natures.
Keywords: Organic–inorganic hybrid; Hydrothermal method; Sliver; Luminescence;

Construction of HgII complexes containing chelating 2,2′-dipyridylamine ligands: Anion effect, photoluminescence and catalytic activities by Ju Hoon Lee; Hyun Min Park; Seung Pyo Jang; Geun Hee Eom; Jeong Mi Bae; Cheal Kim; Youngmee Kim; Sung-Jin Kim (212-215).
Five new structures of HgII complexes containing Hdpa ligands have been determined. With halides, tetrahedral HgII is constructed by a Hdpa and two chlorides or bromides, and strong hydrogen bonds between amine hydrogen atoms and halide atoms provide dimeric compounds. With benzoates, distorted octahedral HgII is constructed by a Hdpa and two chelating benzoate ligands, and hydrogen bonding and π–π interactions provide a polymeric compound. With nitrates or perchlorates, two dpa ligands bridge two HgII ions, and counter-anions axially coordinate to HgII ions to form a polymeric compounds. In addition, all five HgII complexes showed the intense emissions at room temperature, which are red-shifted compared to the corresponding ligand. Moreover, 3 and 4 have shown efficient catalytic transesterification recation, while 1, 2 and 5 has displayed a very slow conversion.Five new structures of HgII complexes containing Hdpa ligands have been synthesized. All five HgII complexes showed the intense emissions at room temperature, and two of them have shown efficient catalytic transesterification recation.Display Omitted► Five new structures of HgII complexes containing Hdpa ligands have been synthesized. ► Both anion effects and metal effects play very important roles for crystal structures of metal-Hdpa compounds. ► All five HgII complexes showed the intense emissions at room temperature. ► Two of them have shown efficient catalytic transesterification recation.
Keywords: Mercury(II) nitrate; 2,2′-dipyridylamine; Anion effects; Photoluminescence; Transesterification;

Gold(I) complexes of neutral, anionic, and oxidized bis(diphenylphosphino)acetonitrile by Sicelo V. Sithole; Richard J. Staples; Werner E. van Zyl (216-220).
The ligand bis(diphenylphosphino)acetonitrile, (PPh2)2CHCN, (“dppm-CN”), was prepared. The reaction between dppm-CN and [Au(C6F5)(tht)] (tht = tetrahydrothiophene) (molar ratio 1:2) formed an open-ended dinuclear gold(I) complex [(AuC6F5)2(dppm-CN)], 1. The crystal structure showed a linear disposition of dimers with intramolecular Au···Au interactions between the dinuclear units, but despite two distinctly different distances between the gold centers, it is without intermolecular Au···Au interactions. Deprotonation of dppm-CN afforded the anion [(PPh2)2CCN]¯ which reacted with [AuCl(tht)] (molar ratio 1:1) to form a neutral cyclic dinuclear gold(I) complex [Au2{(PPh2)2CCN}2], 2. Complex 2 could also be formed from mono- or bis(phosphine) gold(I) chloride complexes through the making and breaking of Au-P bonds. Reaction between the oxidized, deprotonated form of the ligand, [(P(S)Ph2)2CCN]¯, and [AuCl(PPh3)] (molar ratio 1:1) formed the neutral mononuclear complex [Au(PPh3)(P(S)Ph2)2CCN] 3, with the [AuPPh3]+ fragment bonded to one sulfur atom and a large degree of electron delocalization across the S-P-C-P-S ring. Complexes 13 were all obtained in satisfactory yield (70-90%), and analyzed by single crystal X-ray studies, solution 1H and 31P NMR, IR, and elemental analyses.The ligand bis(diphenylphosphino)acetonitrile was used as a neutral and modified anionic and oxidized version in forming mono- and dinuclear gold(I) complexes of the type [(AuC6F5)2(dppm-CN)], 1, [Au2{(PPh2)2CCN}2], 2, and [Au(PPh3)(P(S)Ph2)2CCN] 3.Display Omitted► First examples of cyclic and open-ended dinuclear gold(I) complexes with dppm-CN ligand. ► Utilizing the dppm-CN ligand in anionic, neutral and oxidized form. ► Unusual intermolecular gold(I)-gold(I) interaction.
Keywords: Gold(I) complexes; bis(diphenylphosphino)acetonitrile; Pentafluorophenyl; Dinuclear; X-ray crystal structures;

An efficient basic catalyst based on a new germanium coordination complex by Zhiyong Fu; Yi Tan; Jie Zhang; Shijun Liao; Dongpo Su; Hengjun Chen; Yue Yu; Junjie Peng (221-224).
The replacement of liquid bases by solid base catalysts is a crucial requirement for sustainable industrial processes. The use of heterogeneous catalysts can improve the overall atom catalytic efficiency of reactions and facilitate the organic separation process. Here, we report the synthesis and characterization of a germanium coordination complex Ge(C3H6ONH2)2(OH)2 (1) . Complex 1 is obtained by hydrothermal synthesis and is crystallized in the monoclinic system, space group P21/c with a = 10.250 (2) Å, b = 9.810 (2) Å, c = 10.360 (2) Å, and β = 100.70 (3)°. Single crystal data indicate that the Ge4 + ion has octahedral coordination geometry surrounded by two 2-hydroxypropylammine molecules. Knoevenagel condensation of benzaldehyde and ethyl cyanoacetate is carried out with compound 1 as solid catalytic support in ethanol at 333 K. Experimental results indicate that it is an efficient base catalyst. The reaction gives a 98% yield for the condensation product.A new solid basic catalyst based on the germanium coordination complex Ge(C3H6ONH2)2(OH)2 is synthesized and characterized. The use of the solid base for Knoevenagel condensation of benzaldehyde with ethyl cyanoacetate gives a high catalytic performance.Display Omitted► A new germanium coordination complex is synthesized and characterized. ► Its structure is characterized by single crystal data. ► Phase purity of the bulk sample is confirmed by XRPD data. ► The solid base is tested as solid catalytic support in the Knoevenagel condensation. ► It affords high basic catalytic performance.
Keywords: Germanium coordination complex; Structure and characterization; Solid base catalyst; Knoevenagel condensation; Heterogeneous catalysis;

Anticancer activity and biophysical reactivity of copper complexes of 2-(benzo[d][1,3]dioxol-5-ylmethylene)-N-alkylhydrazinecarbothioamides by Floyd A. Beckford; Jeffrey Thessing; Alyssa Stott; Alvin A. Holder; Oleg G. Poluektov; Liya Li; Navindra P. Seeram (225-229).
A series of copper complexes were synthesized from benzo[d][1,3]dioxole-5-carbaldehyde (piperonal) thiosemicarbazones (RHpTSC where R = H, CH3, C2H5 or C6H5 (Ph)). The complexes show interesting variations in geometry depending on the thiosemicarbazone; a dinuclear complex [Cu(HpTSC)Cl]2, a mononuclear complex [Cu(RHpTSC)2Cl2] (R = CH3 or C2H5) and another mononuclear complex [Cu(PhHpTSC)(PhpTSC)Cl] was generated. The complexes bind in a moderately strong fashion to DNA with binding constants on the order of 104  M− 1. They are also strong binders of human serum albumin with binding constants near 104  M− 1. The complexes show good in vitro cytotoxic profiles against two human colon cancer cell lines (HCT-116 and HT29) and two human breast cancer cell lines (MCF-7 and MDA-MB-231) with IC50 values in the low millimolar concentration range.A series of copper complexes that show interesting variations in geometry was synthesized from benzo[d][1,3]dioxole-5-carbaldehyde (piperonal) thiosemicarbazones. The complexes show good in vitro cytotoxic profiles against human colon and breast cancer cell lines.Display Omitted► Structural variety among copper(II) thiosemicarbazone complexes. ► The complexes are moderate binders of DNA. ► The complexes also bind strongly to human serum albumin. ► Complexes show anticancer behavior that is not linked to DNA binding.
Keywords: Human serum albumin; Thiosemicarbazones; Anticancer; DNA binding; Structural variation;

A practical innovative method for highly chemoselective oxidation of alcohols to the aldehyde and ketones and sulfides to the sulfones using tetra-n-butylammonium peroxomonosulfate (n-Bu4NHSO5) catalyzed by simple water-insoluble copper (II) phthalocyanine (CuPc) in neat water has been developed. Organic co-solvents, surfactants, co-catalyst and hydrophilic auxiliaries were completely missed in this heterogeneous catalytic strategy. The CuPc catalyst and by-product of oxidant (TBAHSO4) could easily be recycled and reused without loss of activity providing readily scalability.The catalytic performance of water-insoluble copper(II) Phthalocyanines in the selective oxidation of alcohols and sulfides using aqueous solution of TBAOX in the absence of organic co-solvents and surfactants was established.Display Omitted► Hydrophobic Cu(II) phthalocyanine catalyzes oxidation reactions in neat water. ► The reactions proceed well in the absence of organic co-solvents and surfactants. ► The catalyst can be easily recycled and reused without loss of activity.
Keywords: Phthalocyanine; Water; Oxidation; Peroxymonosulfate; Alcohol; Sulfide;

In this paper we report the enzymatic properties of Ti-doped CeO2 nanoparticles. The superoxide dismutase activity of Ti-doped nanoparticles is reduced in comparison to undoped nanoceria. In contrast, the oxidase activity of these nanoparticles was unchanged. The change in enzymatic activity was accompanied by a dramatic change in shape to a spherical nanostructure. In addition to reporting a new type of enzymatically-active nanoparticle, Ti-doped cerium oxide nanoparticles are well suited for biological applications.This illustrates the catalytic activity of CeO2 nanoparticles and the effect of Ti doping.Display Omitted► CeTiO2 nanoparticles exhibit enzymatic activities. ► Ti doping reduces the superoxide dismutase activity of doped cerium oxide nanoparticles. ► Ti doping of cerium oxide nanoparticles does not reduce oxidase activity.
Keywords: Nanoparticles; Nanoceria; Enzymatic activity; Metal oxides;

Two supramolecular Keggin polyoxometalate compounds with sandwich-type structure, [Cu4(pz)6][SiW12O40]∙2H2O (1) and [Ag2(pz)2][Ag2(pz)(H2O)2(SiW12O40)] (2)(pz = pyrazine), have been synthesized by in situ generation of pyrazine ligand from pyrazine-2,3-dicarboxylic acid (H2pzdc) under hydrothermal conditions and characterized by IR spectroscopy and TGA. In 1 the combination of CuI ions and pz creates a honeycomb 2-D layer, these layers sandwich [SiW12O40]4 − anions, constructing a multi-sandwich supramolecular compound. In 2 a 2-D layer is formed from [Ag2(pyrazine)2∙(H2O)2]n 2n + and [SiW12O40] n 4n and the layers sandwich 1-D [Ag2-(pyrazine)2]n 2n + linear chains to construct another multi-sandwich supramolecular compound. The pyrazine molecules in 1 and 2 are the product of decarboxylation reaction of pyrazine-2,3-dicarboxylic acid catalyzed by Keggin polyoxometalates. Two compounds show the similar intense fluorescent emissions in the solid state.Two supramolecular compounds with sandwich-type, based on [SiW12O40]4 − clusters with different transition metal were synthesized by the decarboxylation reactions of aryl carboxylic acids, accidentally.Display Omitted► Two supramolecular Keggin polyoxometalate compounds with sandwich-type were hydrothermally synthesized. ► The two compounds showed similar intense fluorescent emissions in the solid state. ► The cases of hydro(solvo)thermal decarboxylation of the polybasic carboxyl groups from aryl carboxylic acids.
Keywords: Keggin polyoxometalates; Transition metal; Catalysis; Decarboxylation reactions; Fluorescence;

Two isostructural coordination polymers, [Zn(dci)2(H2O)2]n (1) and [Mn(dci)2(H2O)2]n (2) (Hdci = 4, 5-dicyanoimidazole), have been synthesized by conventional solution reactions and characterized by IR spectra, elemental analyses and single-crystal X-ray diffractions. In both complexes, the metal ion (ZnII for 1 and MnII for 2) is surrounded by four dciˉ ligands and two coordinated aqua in a distorted N4O2 octahedral geometry. The dciˉ anion adopts a new coordination mode of μ 2-(N, Nʺ) through its neighbouring imidazole nitrogen and cyano nitrogen atoms, and connects adjacent metal ions together, thus forming the 1D double-stranded chain structures 1 and 2. The solid-state fluorescence measurements for 1 and magnetic properties for 2 have been discussed.Two isomorphous coordination polymers [Zn(dci)2(H2O)2]n (1) and [Mn(dci)2(H2O)2]n (2) have been synthesized and characterized. The X-ray single-crystal analyses show that they are 1D double-stranded chain structures formed by a new coordination mode of dciˉ ligand. The fluorescent properties for 1 and magnetic measurements for 2 are studied.Display Omitted► Two isostructural complexes 1 and 2 based on 4, 5-dicyanoimidazole are described. ► They both shows 1D double-stranded chain structures along the c-axis. ► The dciˉ ligand adopts a new coordination mode of μ 2-(N, Nʺ) in 1 and 2. ► The photoluminescence for 1 and magnetic properties for 2has been discussed.
Keywords: 4, 5-dicyanoimidazole; Zinc; Manganese; Coordination polymer; Fluorescence; Magnetic properties;

DNA interaction and in-vitro antibacterial studies of fluoroquinolone based platinum(II) complexes by Mohan N. Patel; Deepen S. Gandhi; Pradhuman A. Parmar (248-251).
A series of square planar complexes of the type [Pt(FQ)2] (where FQ is deprotonated fluoroquinolone family drug) has been synthesized and characterized. The synthesized complexes have been checked for their in-vitro antimicrobial activity against two Gram(+ ve) and three Gram(− ve) bacterial species. Intrinsic binding constant (K b) and mode of binding of complexes toward Herring Sperm DNA (HS DNA) have been determined using absorption titration and viscosity measurement, suggesting the partial intercalative mode of binding. Cleavage ability of complexes has been checked using gel electrophoresis technique and the result shows that the synthesized complexes cleave the DNA more efficiently compared to their respective fluoroquinolones and metal salt.The bulkiness and non-planarity of the fluoroquinolones affect the K b values. The complexes binds to DNA via partial intercalative mode of binding. Absorption titration and viscosity measurement supports the same binding mode. The DNA cleavage efficiency of the complexes are in competition with metal salt and fluoroquinolones.Display Omitted► Synthesis of Pt(II) complexes with fluoroquinolones. ► Characterization by elemental analysis, IR, UV–visible, TGA, mass spectrometry. ► All Pt(II) complexes have been tested for their antibacterial studies. ► The interaction of complexes with DNA has been performed.
Keywords: Square planar; Fluoroquinolone; FAB-MS; HS DNA; Intercalation;

An unprecedented T4(1)4(2)5(2) water topology by Xiao-zhao Tian; Yu-mei Song; Gong-ming Sun; Hai-xiao Huang; Wen-yuan Xu; Xue-feng Feng; Feng Luo (252-255).
Herein, a special water cluster was observed in a metal-organic framework, namely [Zn(μ-(H2O)2)(L)(BDC)]·5H2O (1, L = 2-(pyridine-4-yl)-1H-benzo[d]imidazole, H2BDC = terephthalic acid). In this ice-like water cluster, tetramer water clusters are combined together by sharing one corner to give rise to the T4(1) water structure, while the pentamer water clusters are located on two sides of this T4(1) water chain by sharing two edges with two tetramer water clusters, thus resulting in the overall T4(1)4(2)5(2) water topology.A special water cluster was observed, where tetramer water clusters are combined together to create the T4(1) water structure, while the pentamer water clusters are located on two sides of it, thus resulting in the overall T4(1)4(2)5(2) water topology.Display Omitted► Presented here is a highly rare water structure. ► Both tetramer and pentamer water are contained. ► It is defined as T4(1)4(2)5(2) water topology.
Keywords: Hydrothermal synthesis; Zn(II) compound; Water structure;

Three novel complexes, [Cu(phen)(oba)]2·(DMF)2(H2O) (1), {[Cu(2,2-bipy)2(Hoba)][Cu(2,2-bipy)2(oba)]2·(nitrate)(H2O)13} (2) and [Cd(oba)(ptca)]·(DMA)2 (3) (H2oba = 4,4′-oxydibenzoic acid, H2ptca = terephthalic acid, 2,2-bipy = 2,2′-dipyridylamine, DMA = dimethylamine, phen = 1,10-phenanthroline) have been synthesized and characterized by elemental analysis, infrared spectrum and X-ray crystal diffraction. Strong hydrogen bonds play central roles in the formation of the 3D structure, the combined influence of the weak interactions such as C–H…O, carbonyl…π and C–H…π interactions are also evident in the structures. Complex 1 shows 1D helix structure which is shaped by intermolecular and intramolecular π…π stacking. Complex 2 displays a interesting water morphology based on the lattice water molecules while Complex 3 shows 2-fold (4,4)-net vertical interpenetrating structure. The preliminary investigations on the fluorescence property of the complexes are presented.The two-dimensional structure and the two interpenetrating 2D nets in the structure were formed.Display Omitted► Novel lattice water tape contained in complex 2. ► Ellipse-like channels were observed along c-axis in complex 2. ► Compound 3 is constructed from 2D (4,4) layers with interpenetrated structure.
Keywords: C–H…π; Carbonyl…π; Hydrogen bonds; Interpenetrate;

Nickel nanoparticles (2–6 nm) were successfully deposited on MOF-5 (Zn4O(BDC)3, BDC = 1,4-benzenedicarboxylate) by a facile wet impregnation strategy to prepare Ni@MOF-5 employing Ni(acac)2 (acac = acetylacetonate) as the precursor in absolute ethanol solvent owing to the sensitivity to the moisture of MOF-5. Ni@MOF-5 exhibited excellent catalytic activity for hydrogenation of C = C bond using crotonaldehyde as a probe molecule under mild reaction conditions (conversion > 90.0%, selectivity > 98.0%, 2.0 MPa, 100 °C, 40 min). In addition, the catalyst could be reused and the structure of MOF-5 framework was still maintained. Therefore, MOF-5 promised a novel candidate of support for hydrogenation catalyst.The catalyst Ni@MOF-5 was successfully prepared by wet impregnation strategy, and exhibited much higher catalytic activity in hydrogenation for crotonaldehyde compared with that of the industrial catalyst Ni/SiO2.Display Omitted► Nickel nanoparticles were deposited on MOF-5 by wet impregnation strategy. ► Nickel nanoparticles were probably bonded to the outer surface of the support. ► Ni@MOF-5 exhibited very high catalytic activity in hydrogenation for crotonaldehyde. ► The catalyst could be reused several times with the maintenance of MOF-5 structure.
Keywords: Wet impregnation strategy; Ni@MOF-5; Crotonaldehyde; Hydrogenation;

A novel dinuclear nickel(II) complex, [Ni2L(NO3)(H2O)3]NO3 (where L is a ‘side-off’ compartmental ligand obtained by [1 + 2] condensation of 1,3-diaminopropane and 2,6-diformyl-4-tert-butylphenol) has been synthesized and characterized by routine physicochemical techniques as well as by X-ray single crystal structure analysis. Structure determination reveals that the two nickel ions, separated by 3.0824(9) Å, occupy the N2O2 and O4 compartments of the Schiff base ligand. The immediate coordination environment of each nickel ion is octahedral and the species adopts an umbrella bowed conformation. The catalytic activity of the complex for the oxidation of 3,5-di-tert-butylcatechol to the corresponding o-quinone in methanol solvent has been studied by UV–vis spectroscopic technique.Synthesis and structural characterization of a dinuclear nickel(II) complex of a “side-off” compartmental ligand belonging to the family of organic molecules N,N′-alkylenebis(3-formyl-5-alkylsalicylaldimine) have been carried out and its catalytic activity towards the oxidation of 3,5-DTBC has been investigated.Display Omitted► Synthesis of a dinuclear nickel(II) complex of a phenol based macroacyclic ligand. ► The complex adopts an umbrella bowed conformation. ► The macroacyclic ligand complex shows catecholase like activity. ► The complex exhibits very high turn over number (k cat= 1.5×103 h-1).
Keywords: Nickel complex; ‘Side-off’ compartmental ligand; Crystal structure; Catecholase activity; UV–vis spectroscopy;

Unprecedented formation of a doubly bridged μ-peroxo-μ-pyrazolyldicarboxylato-dicobalt(III) complex by Febee R. Louka; Lam T. Nguyen; Jörg H. Albering; Franz A. Mautner; Salah S. Massoud (269-271).
The reaction of an aqueous solution containing Co(ClO4)2, di(2-pyridymethyl)amine (DPA) and 3,5-pyrazole dicarboxylate anion (Hpzdc2 −) afforded the unprecedented diamagnetic dicobalt(III)-peroxo complex [Co2(DPA)2(μ-pzdc)(μ-η11-O2)]ClO4·3H2O (1) where the pyrazole group was fully deprotonated. The complex was structurally characterized by IR and UV–vis spectroscopy. X-ray crystal structure of 1 reveals the existence of the doubly bridged nature of cis-μ-η11-peroxo (end-on) and the dicarboxylato pyrazole. The peroxo O–O and the Co⋯Co distances are 1.406(3) and 3.7632(5) Å, respectively, and the Co(III) centers are almost co-planar with the pzdc anion.The doubly bridged peroxo and dicarboxylato pyrazole dicobalt(III) complex [Co2(DPA)2(μ-pzdc)(μ-η11-O2)]ClO4·3H2O (1) was synthesized and structurally characterized by spectroscopic techniques and by single-crystal X-ray crystallography.Display Omitted► Peroxo-bridged dinuclear cobalt(III) complex ► Spectroscopic characterization of the complex ► X-ray crystal structure of the complex
Keywords: Cobalt; Bridging peroxo; Crystal structure; Dinuclear complexes;

The first supramolecular water–borate–carbonate anionic rosette ribbon sandwiched by a Ag(I) cationic sinusoidal layer by Geng-Geng Luo; Dong-Liang Wu; Li Liu; Jiu-Xu Xia; Dong-Xu Li; Cheng Peng; Zi-Jing Xiao; Jing-Cao Dai (272-276).
The ultrasonic reaction of Ag2O, 1,3-bis(4-pyridyl)propane (bpp) and Na2B4O5(OH)4·8H2O (borax) under ammoniacal medium gave rise to an unexpected 3D Ag(I) supramolecular sandwich lamellar framework, {[Ag2(bpp)2(H2O)2]·[(H3BO3)3(CO3)·2H2O]} n (1), which consists of 2D silver-bpp cationic host and water–borate–carbonate anionic guest layers. The present 2D anionic layer is formed by fused H2O–H3BO3–CO3 2 − anionic rosette ribbons, in which H3BO3 is obtained via in situ hydrolysis of borax and CO3 2 − derived from absorption of CO2 in air. Interestingly, an unprecedented [CO3 2 −·3(H3BO3)] hydrogen-bonding aggregate having the shape of one concave three-leaved propeller is found in the anionic rosette ribbon.The title compound features a 3D supramolecular sandwich architecture that consists of 2D silver-bpp cationic layers and water-borate-carbonate anionic layers. The anionic layer is formed by fused H2O–H3BO3–CO3 2 − anionic rosette ribbons. The first hydrogen-bonding aggregate [CO3 2 −·3(H3BO3)] shaped-like one concave three-leaved propeller is found in the anionic layer.Display Omitted► The Ag(I) compound containing the H2O–H3BO3–CO3 2− anionic rosette ribbons was synthesized. ► The first [CO3 2−·3(H3BO3)] hydrogen-bonding aggregate is found in the compound.
Keywords: Rosette ribbon; CO3 2 − ions; H3BO3; Hydrogen bonds; Supramolecular chemistry;

Synthesis of [Ru(II)(Tp)(Cl)(PPh3)(CH3CN)] and its reactions with selected terminal alkynes: Experimental and computational studies by Tsang-Hsiu Wang; Wen-Lin Huang; Li-Yu Huang; Ming-Che Li; Pei-I Hsiao; Yu-Wen Yang; Wei-Chen Sun; Yih-Hsing Lo; Chia-Her Lin; Hsin-Pei Chen (277-280).
The ruthenium complex [Ru(II)(Tp)(Cl)(PPh3)(CH3CN)] (3) [Tp = hydrotris(pyrazolyl)borate] contains substitutional ligands, acetonitrile and chloride, and serves as a starting material for the synthesis of new ruthenium complexes. We found that water was also involved in reactions and formed the alkenyl ketone compound [Ru(Tp)(PPh3)(C(CH2Ph) = CHC(O)Ph)] (4) and the acyl complex [Ru(Tp)(PPh3)(C(O)CH2(C6H5)F)] (5). We suggest that water could be an impurity in the solvent, methanol. Methanol cannot be purified before a synthesis procedure, and water is more reactive than methanol. In order to have a better understanding on those new ruthenium complexes, the density functional theory (DFT) has been carried out at the PBE/DZVP level on the proposed mechanisms of the selected reactions. For the reactions of compound 3 with methyl propiolate or ethyl propiolate in the presence of methanol, the solvent can be the nucleophile, and a similar observation can be seen if methanol is replaced by ethanol.Display Omitted► Ru(II)(Tp)(Cl)(PPh3)(CH3CN) serves as a starting material for the synthesis of new ruthenium complexes. ► Water is also involved in reactions and formed the alkenyl ketone compound and the acyl complex. ► The density functional theory (DFT) has been carried out at the PBE/DZVP level on the proposed mechanisms of the selected reactions.
Keywords: Acetonitrile; Terminal alkynes; Water; Methanol; Density functional theory (DFT);

A novel 3D open framework constructed by [Co15(PMIDA)6(H2O)12] clusters and BTC ligands by Xiao-Rui Wang; Qing-xiang Jia; Zhi-Hong Liu (281-284).
A new cobalt coordination polymer based on N-(Phosphonomethyl)imino-diacetic acid (H4PMIDA) and 1,3,5-benzenetricarboxylate acid (H3BTC) ligands, [Co15(PMIDA)6(BTC)2(H2O)12]·6H2O, has been synthesized under hydrothermal conditions, and characterized by elemental analysis, FT-IR spectroscopy, thermal analysis, and single crystal X-ray diffraction. The structure of the complex features a cubic 3D open framework constructed by [Co15(PMIDA)6(H2O)12] cluster and BTC ligand. The magnetic properties of this compound were also investigated.A new cobalt coordination polymer based on N-(Phosphonomethyl)imino-diacetic acid (H4PMIDA) and 1,3,5-benzenetricarboxylate acid (H3BTC) ligands has been synthesized, which features a cubic 3D open framework constructed by [Co15(PMIDA)6(H2O)12] cluster and BTC ligand.Display Omitted► A new cobalt coordination polymer,[Co15(PMIDA)6(BTC)2(H2O)12]·6H2O, has been synthesized. ► Its structure features a cubic 3D open framework constructed by [Co15(PMIDA)6(H2O)12] cluster and BTC ligand. ► The magnetic properties of this complex were investigated.
Keywords: Cobalt coordination polymer; Mixture ligands; Hydrothermal synthesis; Crystal structure; Magnetic properties;

A hexanuclear antiferromagnetic cobalt(II) wheel: Synthesis, structure and magnetic properties by Yunsheng Ma; Fengfeng Xue; Xiaoyan Tang; Bin Chen; Rongxin Yuan (285-287).
The reaction of 6-chloro-2-hydroxypyridine (Hchp) with Co(ClO4)2·6H2O in CH3CN, afforded a hexanuclear complex [Co6(chp)12(H2O)6]. In the structure, adjacent Co2+ ions are bridged by chp ligands into a wheel. Variable-temperature magnetic susceptibility studies reveal that the complex shows antiferromagnetic coupling between the metal ions.In the structure of [Co6(chp)12(H2O)6], six Co2+ ions and six chp ligands construct a planar 12-membered ring based on the Co–O–Co linkage. The magnetic properties were studied by three modes and antiferromagnetic coupling between the metal ions were observed.Display Omitted► We synthesized and characterized the compound [Co6(chp)12(H2O)6]. ► Six Co2+ ions and six chp ligands construct a planar 12-membered ring. ► The magnetic data were studied by three models. ► Antiferromagnetic coupling between the metal ions were observed.
Keywords: Cobalt; Wheel structure; Magnetic property;

Effect of metal ions on the structures of metal–organic frameworks based on mixed ligands by Lian-Jie Li; Xin-Long Wang; Liang Zhao; Kui-Zhan Shao; Hai-Ning Wang; Gang Yuan; Zhong-Min Su (288-291).
Two metal–organic frameworks, namely, [Zn(L)(phen)(H2O)]n (1) and [Cd(L)(phen)]n (2), where H2L = 2,2′-(naphthalene-1,5-diylbis(oxy))diacetic acid and phen = 1,10-phenanthroline, have been synthesized under hydrothermal conditions and characterized by single crystal X-ray diffraction analyses, powder X-ray diffraction and thermogravimetric analysis. Compound 1 can be described as a 3D supramolecular architecture formed via the strong π–π interactions. While, compound 2, obtained by changing the metal ions, exhibits a 3D metal–organic frameworks of PtS topology with the square window (the dimensions is 11.454 × 25.847 Å). The different structures between 1 and 2 indicate that metal ions have significant effects on the final complexes. Moreover, compounds 1 and 2 show good luminescent properties in the solid state at room temperature.Compound 1 shows a 1D chain structure. Compound 2 exhibits the 3D metal-organic frameworks of PtS topology. The different structures between 1 and 2 indicate that metal ions have significant effects on the final complexes.Display Omitted► Compound 1 shows a 3D supramolecular architecture formed via the strong π–π interactions. ► Compound 2 exhibits a 3D network of PtS topology. ► The different structures of 1 and 2 indicate that metal ions have significant effects on the final complexes.
Keywords: Metal–organic frameworks; Hydrothermal synthesis; Crystal structure; Luminescent property;

A novel sandwich-type europium-substituted germanomolybdate linked with coordination cation [Cu(en)2]2+ by Lan-Jun Yang; Lin Xu; Feng-Yan Li; Yu-Chao Wang; Bing-Bing Xu (292-296).
A sandwich-type europium-substituted germanomolybdate, H(H2en)5[Cu(en)2] [Eu(GeMo11O39)2]·11H2O (1) (en = ethylenediamine) has been synthesized and structurally characterized by elemental analysis, IR spectroscopy, UV electronic spectroscopy, thermogravimetric analysis and single crystal X-ray diffraction. Complex 1 displays a one-dimensional zigzag chain framework built up from the [Eu(GeMo11O39)2]13− polyanions alternatively linked by [Cu(en)2]2+ cations. The photoluminescence property of solid samples for compound 1 has been investigated, and the spectrum exhibits obvious red fluorescence. The magnetic investigation on complex 1 indicates that the magnetic behavior attributes to a combined effect of depopulation and intermolecular antiferromagnetic interactions.An organic–inorganic hybrid europium-substituted sandwich-type germanomolybdate, H(H2en)5[Cu(en)2] [Eu(GeMo11O39)2]·11H2O (1) (en = ethylenediamine) exhibits a one-dimensional zigzag chain structure formed by the [Eu(GeMo11O39)2]13− polyanions alternatively linked by [Cu(en)2]2+ cations.Display Omitted► A new organic–inorganic hybrid germanomolybdate exhibits one dimensional chain. ► The luminescence of compound 1 displays obvious red fluorescence. ► The depopulation and intermolecular antiferromagnetism affect the magnetic behavior.
Keywords: Germanomolybdate; Europium; Sandwich-type; Photoluminescence; Magnetic property;

We report a novel successful one pot preparation of Keggin-type (CTA)3PMo12O40 (CTA = cetyltrimethylammonium cation) hybrid nanomaterial by microemulsion method. The (CTA)3PMo12O40 nanoparticles was formed by direct addition of aqueous solution of hydrochloric acid to reverse micelles containing Na2MoO4 and Na2HPO4. The product was found to be nearly uniform spherical nanoparticles with 20–30 nm size.Keggin type (CTA)3PMo12O40 hybrid nanomaterial was synthesized by using a microemulsion system. The physicochemical characterizations showed uniform size of about 25 nm and spherical morphologies of synthesized nanomaterial.Display Omitted►(CTA)3PMo12O40 hybrid nanomaterial was synthesized by multicomponent reaction. ►The reverse micelles provide nanoreactors for preparation of nanoparticles. ►The nanoparticles have uniform size of about 25 nm and spherical morphologies.
Keywords: Keggin; Phosphomolybdate; Nanomaterial; Hybrid; Microemulsion;

Use of a C 3-symmetric facial ligand N,N’,N”-tris(3-pyridyl)-1,3,5-benzenetricarboxamide (L1), three porous MOFs, [CdCl2(aas-L1)]n (1), [HgI2(sss-L1)]n (2) and [CoCl2(ass-L1)(EtOH)]2 (3), were obtained under solvothermal conditions. Complex 1 exhibits a fascinating 2D two interwoven nets consisting of sandwich-like channels. Compound 2 shows an infinite 1D polymeric chain in herringbone fashion running along a-axis. The hydrogen-bonding interactions further link the molecules into 2D extended structure with 48-membered macrocycles. In the binuclear complex 3, two metal centers are bridged by two ligands, producing a 28-membered ring. The macrocyclic subunits further self-assemble into an open-framework structure with porous system via the hydrogen-bonding interactions. Furthermore, the luminescence properties of these compounds have been studied.Three porous MOFs have been hydrothermally synthesized via the reaction of a C 3-symmetric facial ligand L1 and MX2 (M = Cd, Hg and Co) under different temperature. Sing crystal X-ray diffraction revealed that complex 1 exhibits a fascinating 2D two interwoven nets consisting of sandwich-like channels. Compounds 2 shows an infinite 2D extended structure with 48-membered macrocycles via the hydrogen-bonding interactions. However, Complex 3 exhibits an open-framework structure with 28-membered macrocycles. The luminescence properties of them were also investigated at room temperature in the solid state.Display Omitted► Three MOFs based on a C 3-symmetric triangular facial ligand have been synthesized. ► Complex 1 exhibits 2D two interwoven nets with unique (3,4,6)-connected topology. ► Hydrogen bonding interactions are driving force for the construction of MOFs. ► Coordiantion polymers 1 and 2 possess strong luminescence.
Keywords: Supramolecular complexes; Tripodal ligand; Crystal Structure; Fluorescence properties;

A novel complex {[Cu12(4,4´-bpz)12(H2Mo8O28)3/2(Mo8O26)3/2]·3(H3O)} n (1) has been hydrothermally synthesized from the self-assembly of CuSO4, H2MoO4 and 4,4´-H2bpz [4,4´-bpz = 3,3´,5,5´-tetramethyl-substituted 4,4´-bipyrazole] and H2O. Its structure is composed of rare (CuL) castellated chains that are linked by two kinds of molybdenum-oxide clusters to form an unusual two dimensional 3-fold interpenetrated structure. Photoluminescent investigation reveals that the title complex displays a strong blue-light emission.A novel polyoxometalate-containing metal–organic hybrid compound with unusual 3-fold interpenetration (6.3) topology was synthesized, which is the first example included two kinds of molybdenum oxide anion clusters [Mo8O26]4 − and [Mo8O26(OH)2]6 −.Display Omitted► A novel polyoxometalate-containing metalorganic hybrid compound with unusual 3-fold interpenetration 2-D (6.3) topology was synthesized. ► It is the first example which included two kinds of molybdenum anion clusters [Mo8O26]4 − and [Mo8O26(OH)2]6 − ► It exhibits two kinds of photoluminescent emission.
Keywords: Copper; Crystal structure; Molybdenum-oxide; Topology; Photoluminescence;

Reaction of [Me4N]2[Cd(SPh)4] and [Ag(PPh3)2NO3] (molar ratio = 1:1) in MeOH/CH2Cl2 (1:1) followed by recrystallization from DMF/Et2O yielded a neutral heptanuclear cluster, [Cd3(μ-SPh)63-SPh)4Ag4(PPh3)4] (1), while interaction of [Me4N]2[Cd(SPh)4] with AgNO3 and dppp (molar ratio = 4:6:3) gave a neutral undecanuclear cluster [Cd3(OMe)2(μ-SPh)43-SPh)8Ag8(μ-dppp)4] (2). Crystal structures and photoluminescent properties of the two clusters in solid state were reported.Two neutral heterometallic cadmium(II)/silver(I) clusters of phenylthiolates, a heptanuclear [Cd3(μ-SPh)63-SPh)4Ag4(PPh3)4] and a undecanuclear [Cd3(OMe)2(μ-SPh)43-SPh)8Ag8(μ-dppp)4] with phosphine ligands, were synthesized and structurally characterized.Display Omitted► Polynuclear Cd(II)/Ag(I) heterobimetallic clusters of phenylthiolates. ► Reaction of the homolepic [Cd(SPh)4]2– anion with silver(I) ion. ► The design and syntheses of polynuclear heterometallic clusters based on [Cd(SPh)4]2– as a metalloligand in the photoluminescenct application.
Keywords: Cadmium(II); Silver(I); Thiolate ligand; Cluster; Crystal structure; Photoluminescent property;

A trinuclear complex [CuII 2(bpmen)2][MoIV(CN)8]∙8H2O was synthesized and structurally characterized, crystallized in the monoclinic system, space group Cc with cell constants a  = 11.726(2)Å, b  = 17.158(3)Å, c  = 23.891(5)Å, β  = 97.96(3)° and Z = 4. It exhibited thermally reversible photo-responsive properties on UV light irradiation through a MoIV to CuII charge transfer, which is potential interest for the molecular storage of information as a multifunctional molecule-based material.A trinuclear-cluster complex [CuII 2(bpmen)2][MoIV(CN)8]∙8H2O was synthesized and exhibited thermally reversible photoresponsive properties on UV light irradiation through a MoIV to CuII charge transfer.Display Omitted► Synthesis and structure of a Mo–Cu trinuclear-cluster complex. ► The photoinduced charge transfer from MoIV(S = 0) to CuII (S = 1/2). ► Thermally reversible photoresponsive materials.
Keywords: Crystal structure; Trinuclear complex; Molecule-based materials; Photomagnetic property; Charge transfer;

Structure and Dual Emission of a Heteropentanuclear Er4Yb Complex by Hai-Bing Xu; Jian-Guo Deng; Zhong-Ning Chen (314-316).
By virtue of versatile coordination modes of 8-hydroxyquinoline and acetate, a new mixed lanthanide complex Er4Yb, {[Er2(hfac)43-CH3COO)(μ3-OH)]2}{μ-HMq}2{Yb(hfac)(μ4-CH3COO)2} (hfac  = hexafluoroacetylacetonate; HMq = 2-methyl-8-hydroxyquinoline) was isolated. The luminescence measurements show that upon irradiation with [n  →  π*] absorption of HMq at λ ex  = 400 nm, “dual emission” from both erbium (III) and ytterbium (III) has been achieved, respectively.A new heteronuclear bimetallic complex Er4Yb was prepared and characterized by X-ray crystallography. Irradiating with λ ex  = 400 nm, “dual emission” from both erbium (III) and ytterbium (III) has been observed.Display Omitted► A new mixed lanthanide cluster Er4Yb is isolated by a simple synthetic procedure. ► Two ErIII-fragments are linked to the central YbIII ion in a symmetric fashion. ► “Dual emissions” from both erbium (III) and ytterbium (III) are observed by irradiation.
Keywords: Bimetallic; Erbium; Ytterbium; Dual emission; Luminescence;

Two three-dimensional (3D) chiral frameworks, [Cd6(L)4(d-Cam)4(H2O)4]·2H2O (1D) and [Cd6(L)4(l-Cam)4(H2O)4]·2H2O (1L) [HL = 3,5-di(imidazol-1-yl)benzoic acid, d-H2Cam =  d-camphoric acid, l-H2Cam =  l-camphoric acid], have been synthesized under hydrothermal conditions, which represent a nice example of enantioselectivity of organic racemic ligands (dl-camphorates) during the self-assembly process and formation of the metal complexes. Compounds 1D and 1L feature 3D framework with chiral chains constructed by Cd(II) cations and camphorate anions. Solid-state circular dichroism (CD) spectra of 1D and 1L revealed that they are enantiomers. Furthermore, the complex with chiral C2 space group displays ferroelectric behavior with a remnant electric polarization (P r) of ~ 0.140 μC/cm2 and an electric coercive field (E c) of ~ 17.11 kV/cm.Racemic camphorates (dl-Cam2 −) were resolved into two homochiral enantomers in the formation of three-dimensional Cd(II) frameworks with 3,5-di(imidazol-1-yl)benzoate, which provide a nice example of resolution of dl-H2Cam without chiral template.Display Omitted► Homochiral three-dimensional cadmium(II) framework. ► Complex with camphoric acid and 3,5-di(imidazol-1-yl)benzoic acid. ► SHG and ferroelectric property of the complex.
Keywords: Hydrothermal synthesis; Racemic camphoric acid; Homochiral cadmium(II) framework; SHG; Ferroelectric property;

A bis-C (cage)-substituted o-carborane 1,2-bis (3-butenyl)-1,2-dicarba-closo-dedocaborane is successfully synthesized via cross-coupling reaction of carboranyl Grignard reagent with allyl bromide in the presence of copper (I) salt as catalyst. The optimization of this cross-coupling reaction reveals that the copper (I) salts have high catalytic activity for the formation of the corresponding dialkenyl-substituted o-carborane, especially in the presence of 1-phenyl-1-propyne as additive, whereas the palladium and nickel complexes containing triphenylphosphine ligands favor the formation of mono-substituted alkenylcarborane.Alkenylcarborane derivatives were synthesized by trans-metal catalyzed cross-coupling reaction of carboranyl grignard reagent 2 with allyl bromide. Bis-substituted compound 4 was obtained in good yield by copper catalyst in the presence of 1-phenyl-1-propyne, whereas palladium and nickel complexes containing triphenylphosphine ligands were available for the formation of mono-substituted alkenylcarborane 5.Display Omitted► 1,2-bis (3-butenyl)-1,2-dicarba-closo-dedocaborane was synthesized. ► Compound was obtained by Cu (I)-catalyzed cross-coupling reaction. ► The Cu (I) salt had good catalytic activity. ► Pd and Ni complexes bearing phosphine ligands had good selectivity. ► The yield of Cu (I)-catalyzed cross-coupling reaction was improved by the use of 1-phenyl-1-propyne.
Keywords: Copper catalyzed; Cross-coupling; Alkenylcarborane; Optimization;

Corrigendum to “Novel hexamercaptotin: Synthesis and characterization of [N(CH3)4]2Sn(SH)6 and [N(C2H5)4]2Sn(SH)6 complexes” [Inorg. Chem. Commun. 4(11) (2001) 643–647] by Jing-Cao Dai; Li-Ming Wu; Chuan-Peng Cui; Zhi-Yong Fu; Sheng-Min Hu; Wen-Xing Du; Wen-Jian Zhang; Xin-Tao Wu (324).