Inorganic Chemistry Communications (v.73, #C)

Contents List (iii-xiv).

Photophysical and photocatalytic behavior of nickel(II) 5,10,15,20-tetrakis(1-methylpyridinium-4-yl)porphyrin by Máté M. Major; Ottó Horváth; Melinda A. Fodor; Lajos Fodor; Zsolt Valicsek; Günter Grampp; Alexander Wankmüller (1-3).
Kinetically inert cationic Ni(II)TMPyP4 + (H2TMPyP4 +  = 5,10,15,20-tetrakis(methylpyridinium-4-yl)porphyrin) displayed a characteristic fluorescence (τ = 1.2–1.4 ns, Φ = 2.0 × 10− 3), which was quenched with triethanolamine (TEOA) in a static way. This complex proved to be an efficient photocatalyst in the system containing TEOA and methylviologen (MV2 +) as electron donor and acceptor, respectively. Interestingly, however, deviating from the behavior of the analogous Co(III) and Mn(III) complexes in such a system, TEOA did not dynamically quench the triplet excited state of Ni(II)TMPyP4 + (τ = 6.31 μs), hence no reduction of the metal center occured upon irradiation. Instead, in the presence of this electron donor (at 1 × 10− 3  M) the excited-state lifetime dramatically increased (to τ = 36.6 μs), indicating the formation of a Ni(II)TMPyP4 +-TEOA associate. This longer-lived triplet was efficiently quenched by MV2 + (kq  = 9.9 × 106  M− 1  s− 1), leading to the formation of MV•+. The overall quantum yield of this one-step photoassisted electron transfer is considerably high (Φ = 0.011–0.013 at Soret-band irradiation). Hence, this system, combined with a suitable co-catalyst, may be applicable for visible light-driven hydrogen generation from water.Water-soluble Ni(II)TMPyP4 + displayed characteristic fluorescence and proved to be an efficient photocatalyst in a visible light-driven one-step electron transfer between triethanolamine and methylviologen.Display Omitted
Keywords: Nickel(II) porphyrin; Water-soluble; Fluorescence; Photocatalysis; Triplet state; Static and dynamic quenching;

Alternating copolymerization of CHO and MA catalyzed by the hetero-bimetallic Zn-Yb-Salen complex by Qi Shi; Xiaohui Yang; Xingmei Zhang; Xuekun Li; Juxiang Yang; Xingqiang Lü (4-6).
For the hetero-bimetallic complex [Zn(L)(μ 1-OAc)Yb(μ 1-OAc)(μ 2-OAc)(H2O)] (1; H2L = N,N′-bis(3-methoxy-salicylidene)cyclohexane-1,2-diamine), its character of self-owned normal OAc initiators around two active species endows effective bulk solvent-free copolymerization of CHO (cyclohexene oxide) and MA (maleic anhydride) in the presence of cocatalyst (DMAP, 4-(dimethylamino)-pyridine or TPP, triphenylphosphine) or not. Especially from TPP-assisted controllable copolymerization, perfectly alternating polyesters are obtained.Complex [Zn(L)(μ 1-OAc)Yb(μ 1-OAc)(μ 2-OAc)(H2O)] (1) characteristic of self-owned three OAc initiators around two active species is found to effectively catalyze bulk solvent-free copolymerization of CHO and MA, and its combination with TPP can produce perfectly alternating polyesters from controllable copolymerizations.Display Omitted
Keywords: Hetero-bimetallic-Salen complex; Alternating polyester; Poly(ester-co-ether); CHO and MA; Bulk solvent-free copolymerization;

Hydrolysis kinetics of a sol-gel equilibrium yielding ladder-like polysilsesquioxanes by Albert S. Lee; Seung-Sock Choi; Kyung-Youl Baek; Seung Sang Hwang (7-11).
An investigation into the hydrolysis kinetics of an aqueous base-catalyzed sol-gel reaction yielding ladder-like polysilsesquioxanes was studied using NMR. Under various variables of monomer concentration, water concentration, solvent type, and monomer type, the various effects on molecular weight and degree of condensation were elucidated. Moreover, the various rate orders and rate constants were calculated and compared with previous reports of the hydrolysis of organosilane precursors. Through this study we were able to ascertain the optimal conditions of hydrolysis-polycondensation for obtaining highly condensed, high molecular weight ladder-like polysilsesquioxanes.Hydrolysis kinetics of various organoalkoxysilanes yielding ladder polysilsesquioxanes was studied as a function of monomer concentration and water concentration.Display Omitted
Keywords: Sol-gel chemistry; Hydrolysis-polycondensation; Reaction kinetics; Ladder polysilsesquioxanes;

Two Cd(II) coordination polymers based on 3,6-bis(imidazol-1-yl)carbazole: Syntheses, structures and photocatalytic properties by Hong-Jian Cheng; Yi-Feng Lu; Chen Li; Ye Shu; Ji Ma; Wen-hui Li; Rong-Xin Yuan (12-15).
Hydrothermal reactions of CdCl2·2.5H2O with 3,6-bis(imidazol-1-yl)carbazole (bmcz), 2-amine-1,4-benzenedicarboxylic acid (2-NH2-1,4-H2BDC) or 1,4-naphthalenedicarboxylic acid (1,4-H2NDC) afforded two coordination polymers, [Cd(2-NH2-1,4-BDC)(bmcz)] n (1) and [Cd(1,4-NDC)(bmcz)] n (2). Complexes 1 and 2 were characterized by elemental analysis, IR, powder X-ray diffraction, and single-crystal X-ray diffraction. 1 and 2 are isomorphic and exhibit 3D supermolecular structures. The solid state luminescent and optical properties of 1 and 2 at ambient temperature were also investigated. A comparative study on their photocatalytic activity toward the degradation of methylene blue in polluted water was explored.Two 3D coordination polymers [Cd(2-NH2-1,4-BDC)(bmcz)] n and [Cd(1,4-NDC)(bmcz)] n were generated from solvothermal reactions of 2-amine-1,4-benzenedicarboxylic acid (2-NH2-1,4-H2BDC) or 1,4-naphthalenedicarboxylic acid (1,4-H2NDC) with CdCl2·2.5H2O and 3,6-bis(imidazol-1-yl)carbazole (bmcz). Their solid state luminescent and photocatalytic properties were investigated.Display Omitted
Keywords: Cadmium; Crystal structure; Coordination polymer; 3,6-Bis(imidazol-1-yl)carbazole; Photocatalysis;

Reactions of ZnCl2 with 4′-(2,4-disulfophenyl)-2,2′:6′2″-terpyridine (H2DSPT) result to two new compounds with formula, {[Zn(DSPT)(H2O)2]·2H2O} n (1) and {[Zn(DSPT)(H2O)2]·H2O} n (2), respectively. Compound 1 is a binuclear complex, whereas compound 2 is a mononuclear organozinc compound. The coordination compounds can be controllable synthesized by adjust the pH value. The thermal behavior of 1 was explored by TG and VT-PXRD, which indicated that it undergo crystal-to-crystal transformation manner. Both compounds 1 and 2 show weak luminescence in both solid state and water emulsions compared with H2DSPT. The luminescence intensity of compound 1 can strongly enhanced by the addition of diethylchlorophosphonate (DCP), but significant less influenced by dimethylmethylphosphonate (DMMP), diethylcyanophosphonate (DCNP) and other selected organophosphate, which make compound 1 has potential application on nerve-agent detection.Two new compounds based on a terpyridine-based ligand containing sulfo groups were obtained. The crystal-to-crystal transformation and the ability for detecting nerve agent mimics for selected compounds were explored.Display Omitted
Keywords: Terpyridine-based ligand; Organozinc compound; Crystal-to-crystal transformation; Nerve agent mimics;

Fluorescent selectivity for small molecules of two coordination polymers based on a tetracarboxylate ligand by Xiao Zhang; Xiao-Qing Wang; Xiao-Xiao Wang; Zhi-jia Xue; Tuo-Ping Hu (21-25).
Two coordination polymers [Cd(tptc)0.5(4,4′–bibp)]n (1) and {[Zn3(Htptc)2(phen)2]·1.5H2O}n (2) (H4tptc = terphenyl-3,3″,5,5″-tetracarboxylic acid, 4,4′-bibp = 4,4′-bis(imidazolyl)biphenyl, and phen = 1,10-phenanthroline) were synthesized under solvothermal conditions. Complex 1 displays a 3D structure with a Schläfli symbol of {44.62}{48.620}. Complex 2 possesses a 2D layer network, incorporating [Zn3(COO)6] second building units (SBUs), which is packed into a 3D supramolecular architecture by π ⋯ π interactions. Both of them exhibit strong luminescence characteristics. It is worth to note that complexes 1 and 2 show potential application to detect small organic molecules.Two coordination polymers were synthesized with different metal ions and auxiliary ligand, complexes 1 and 2 show potential application to detect small organic molecules. Complex 1 exhibits efficient fluorescence quenching behavior upon addition of NP, and the complex 2 shows better fluorescence quenching behavior in NA.Display Omitted
Keywords: Terphenyl-3,3″,5,5″-tetracarboxylic acid; Transition-metal coordination polymer; Luminescent sensing;

Rational synthesis of a porous polyhedral metal-organic framework carrier for controllable drug release by Chuying Gu; Fumei Li; Baohong Li; Jingwen Xu; Suzhen Yang; Miaomiao Luo; Jianqiang Liu; Gan Liu (26-29).
A new fabrication of [Cu32-H2O)(PHB)(H2O)]·(DMF)3(H2O)6 (GDMU-2) was synthesized and used as a drug vehicle of 5-Fluorouracil (5-FU) for drug delivery. The incorporation of the drug 5-FU into the GDMU-2 was around 53.7 wt% per gram of dehydrated GDMU-2. Cargo release behavior and material degradation profile were also investigated under different pH. 5-FU is released in a highly controlled and progressive manner with 100% of the drug release after 97 h at acidic condition and with 83% after 132 h at PBS. In vitro cytotoxicity assays indicated that the GDMU-2 possesses no obvious cytotoxicity. The result from this work provides a new avenue for MOF to be used as potential drug delivery.A new POMF was used as a drug vehicle of 5-Fluorouracil (5-FU) for drug delivery. The cargo release behavior and material degradation profile were also investigated under different pH.Display Omitted
Keywords: Polyhedral cage; Topology; Drug delivery;

Mixed (phthalocyaninato)(tetranaphthylporphyrinato) terbium triple-decker complex: Synthesis, crystal structure and magnetic properties by Liguo Yang; Youzhu Yu; Xin Wang; Mengliang Zhu; Qianqian Gao; Yuqiang Dai; Yongzhong Bian (30-33).
Mixed (phthalocyaninato)(tetranaphthylporphyrinato) terbium(III) triple-decker complex [(TNP)Tb(Pc)Tb(TNP)] (1) was synthesized by treating the half-sandwich complex [Tb(TNP)(acac)] (acac = acetylacetonate) with Li2(Pc). Compound 1 represents the first sandwich-type complex containing tetranaphthylporphyrin ligand. This new triple-decker complex was characterized by MALDI-TOF mass, 1H NMR, electronic absorption and IR spectroscopies. The molecular structure was determined by single crystal X-ray diffraction analysis confirming the symmetrical triple-decker structure with two outer TNP ligands and one inner Pc ligand. The static and dynamic measurements for the magnetic properties of complex 1 were conducted. The results indicate the slow relaxation and strong quantum tunneling of magnetization for this symmetrical Tb-Tb magnet.Mixed (phthalocyaninato)(tetranaphthylporphyrinato) terbium triple-decker complex [(TNP)Tb(Pc)Tb(TNP)] (1) was synthesized and characterized by single crystal X-ray diffraction. The magnetic property of the complex was studied.Display Omitted
Keywords: Sandwich complex; Single crystal; Magnetic properties; Porphyrin; Phthalocyanine;

A new compound based on polyoxoniobates and three types of copper complexes by Po-Han Lin; Hai-Yang Guo; Xiao Zhang; Xiao-Bing Cui; Qi-Sheng Huo; Ji-Qing Xu (34-36).
A new compound based on bi-capped Keggin polyoxoniobates and copper coordination complexes, with formula [Cu(en)2][Cu(en)2(H2O)2][Cu(en)2(H2O)]2[H4SiNb12V2O42]·7H2O (1) (en = ethylenediamine), was obtained under hydrothermal condition and characterized by single crystal X-ray diffraction, infrared spectrum (IR), powder X-ray diffraction (PXRD), Ultraviolet–visible spectroscopy (UV–vis) and electron spin resonance (ESR) analysis. Compound 1 has three different types of copper complexes in it. A [Cu(en)2]2 + and two [Cu(en)2(H2O)]2 + fragments were supported by the polyoxoniobate to form a novel polyoxoniobate tri-supported coordination complex.A novel polyoxoniobate tri-supported coordination complex has been hydrothermally synthesized and characterized.Display Omitted
Keywords: Polyoxoniobates; Tri-supported complex; Bi-capped Keggin; Hydrothermal; Single-crystal;

A new 2D Cu(I)-based coordination polymer with Lewis basic sites based on pytpy (pytpy = 4′-(4-pyridyl)-3,2′:6′,3″-terpyridine) ligand, [Cu(pytpy)(CN)]n(1), has been synthesized solvothermally and characterized. The photoluminescence property shows that 1 can work as highly sensitive sensors to nitro explosive and Fe3 + by luminescent quenching. This study demonstrated that 1 could be a useful luminescent sensor for metal ions and organic small molecules.A new 2D Cu(I)-based coordination polymer (CP) with Lewis basic sites-rich based on pytpy (pytpy = 4′-(4-pyridyl)-3,2′:6′,3″-terpyridine) ligand, [Cu(pytpy)(CN)](1), has been synthesized solvothermally. Luminescence properties of 1 were investigated, and the results show that 1 can work as highly sensitive sensors to nitro explosive and Fe3 +. The demonstrated that 1 could be a useful luminescent sensor for metal ions and organic small molecules.Display Omitted
Keywords: Luminescence; Nitro explosives sensing; Quenching efficiency;

A unique 3D entangling Cu(II)-metal organic framework, namely, {[Cu4(abtc)2(btab)6·3H2O]·2H2O}n (1), has been successfully constructed from CuII and 3,3′,5,5′-azo benzene tetracarboxylate building units with the aid of N-donor bridging spacers [1,4-bis(triazol)butane], and directs a rare self-penetrating structure with polyhelix motifs and presents a new (4,4,8)-connected (4.65)2(64.7.8)2(42.620.72.84) topology. The magnetic investigations demonstrate that complex 1 exhibits antiferromagnetic coupling interaction between the adjacent Cu(II) ions.A unique 3D entangling Cu(II)-metal organic framework presents a rare self-penetrating structure with polyhelix motifs and a new (4,4,8)-connected (4.65)2(64.7.8)2(42.620.72.84) topology and exhibits antiferromagnetic coupling interaction between the adjacent Cu(II) ions.Display Omitted
Keywords: Cu(II)-metal-organic framework; Self-penetrating; Polyhelix motifs; Magnetic property;

Isomerization-induced introduction of metal cations into polyoxomolybdate-surfactant hybrid crystals by Keisuke Mikurube; Kimiko Hasegawa; Takashi Matsumoto; Jun Kobayashi; Haruo Naruke; Takeru Ito (45-48).
Monovalent metal cations (Ag+, K+, and Cs+) were successfully introduced into inorganic-organic hybrid crystals composed from β-type octamolybdate (β-Mo8) and hexadecylpyridinium (C16py). The introduction of metal cations was induced by the molecular isomerization from α-Mo8 to β-Mo8 anion. All hybrid crystals consisted of alternate stacking of β-Mo8 inorganic and C16py organic layers. In the inorganic layers, the metal cations and β-Mo8 anions were connected to form one- or two-dimensional arrangement, which depended on the ionic radius of metal cations.Monovalent metal cations were introduced into inorganic-organic hybrid crystals composed from β-type octamolybdate (β-Mo8) and hexadecylpyridinium. The introduction of metal cations was induced by the molecular isomerization from α-Mo8 to β-Mo8 anion. In the inorganic layers, the metal cations and β-Mo8 anions were connected to form one- or two-dimensional arrangement.Display Omitted
Keywords: Inorganic-organic hybrid; Crystal; Surfactant; Polyoxometalate; Isomerization;

Sensing of insulin fibrillation using alkoxy-bridged binuclear rhenium(I) complexes by Veerasamy Sathish; Arumugam Ramdass; Zong-Zhan Lu; Murugesan Velayudham; Pounraj Thanasekaran; Kuang-Lieh Lu; Seenivasan Rajagopal (49-51).
For the first time we report the simple, cost-effective, sensitive detection of human insulin fibrils using an alkoxy-bridged binuclear rhenium(I) complexes by the enhancement in luminescence intensity, emission lifetime and the formation of fibrils. The Re(I) complexes are weakly emissive, when it is dissolved with native insulin in an incubation buffer, but it becomes highly luminescent after the formation of insulin fibrils. This binding of human insulin fibrils is attributed to the hydrophobic as well as π − π stacking interaction of naphthalene moiety present in rhenium(I) complexes.An alkoxy bridged binuclear rhenium(I) complexes as a probe for the detection of aggregation of human insulin fibrils with binding of the complexes that are confirmed by the enhancement of fluorescence intensity, emission lifetime. The formation of fibrils can be supported by microscopic studies.Display Omitted
Keywords: Re(I) complexes; Luminescence enhancement; Insulin fibrils; Hydrophobic; π − π stacking interaction;

Metal cation-dependent helicity of two 1-D heterometal chains constructed from pyridine-2,6-dicarboxylate by Qin Wei; Yu-Jia Ding; Xia Huang; Ji-Yuan Zhang; Wen-Jing Lu; Ren-Feng Dong; Yue-Peng Cai; Li-Ping Si (52-56).
Two interesting 1D heterometal chain-like compounds from pyridine-2,6-dicarboxylic acid (H2PDA) and AgNO3 as well as ZnCl2/SmCl3, namely [ZnAg(PDA)22-H2O)·(H3O)+⋅(H2O)0.25]n (1) and [SmAg(PDA)2(H2O)3·3H2O]n (2), have been solvothermally synthesized by fine control synthetic conditions, and structurally characterized. The results reveal that 1D rac-helical chain 1 containing two independent single-stranded single-helical P-helical and M-helical chains crystallized in the tetragonal I4(1)/a space groups, in which the octahedral Zn2 + center in 1 coordinated to two pyridyl nitrogen atoms and four carboxyl oxygen atoms from two chelating PDA2 − ligands, while the distorted tetrahedral Ag+ center in 1 ligated to two aqueous oxygen atoms and two carboxyl oxygen atoms from two bridging PDA2 − ligands. Under the same reaction conditions except the reactant of SmCl3 replacing ZnCl2, 1-D meso-helical chain 2 with monoclinic P2(1)/n space group, consisting of two adjacent three-stranded single-helical P and M chains connected through Ag―O bonds, was obtained. Each Sm3 + ion in 2 was chelated to two PDA2 − anions as tridentate (ONO) ligands and three water molecules that completed the nine-coordinated environment around Sm3 +. The coordination sphere of Ag+ was finished by five carboxyl O atoms from three PDA2 − ligands with highly distorted trigonal bipyramidal geometry. Obviously, different helicity between 1 and 2 closely related to the radius and coordi numbers of the 3d/4f metal cation ions. Moreover, the fluorescent propeties of compounds 1 and 2 were also studied.Two metal cation-dependent 1-D chains 1–2, in which 1 shows a rac-helicity and 2 a meso-helicity, were hydrothermally synthesized under the same reaction conditions.Display Omitted
Keywords: Metal cation-dependent helicity; Pyridine-2,6-dicarboxylate; rac-/meso-helical chains; Fluorescence;

Three interesting metal-organic frameworks, [(Cd2(Hpidc)(pdc)]n(1), {[(Cd2(Hpidc)2(H2O)]·H2O}n(2), {[(Cd2(Hpidc)2(H2O)]·2H2O}n(3) (H3pidc = pyridine-2-yl-1H-imidazole-4,5-dicarboxylic acid, H2pdc = 2,6-pyridine dicarboxylic acid) have been synthesized under hydrothermal by controlling the temperature and varying with the second organic ligands. Compounds 1 and 2 possess 3D frameworks with a new topological network with 2-nodal (6, 6)-connected net and 2-nodal (5, 6)-connected net respectively. Notably, Compound 3 exhibit a 1-D interesting double Zigzag chain. The thermogravimetric and fluorescence properties of 1–3 were also explored.Six coordinate compounds obtained with various auxiliary ligands.Display Omitted
Keywords: Cd(II); H3pyidc; Template; Luminescent properties;

DNA damage by endogenous/exogenous chemicals and ionizing radiation results in the formation of abasic sites, alkylation products, oxidative lesions and covalent-DNA adducts. The covalent DNA adducts adopt different conformations that might lead to various types of mutations. In the present study, we investigated the interaction of different Ru(II) polypyridyl complex, [Ru(phen)2(dppz)]2 + (phen: 1,10-phenanthroline; dppz: dipyrido[3,2-a:2′,3′-c]phenazine) with oligonucleotide sequences containing either [N-(2′-deoxyguanosin-8-yl)-2-aminofluorene] (AF-dG) or [N-(2′-deoxyguanosin-8-yl)-2-acetylaminofluorene] (AAF-dG) adduct. The modification of the oligonucleotides with the arylamines was characterized by UV–visible and MALDI-TOF spectroscopy. The results of thermal denaturation studies of oligonucleotide with Ru(II) complex indicate that Ru(II) complex stabilize the arylamine adducts better than control oligonucleotide. The integrated luminescence intensity of the Ru(II) complex was increased two-fold in AAF-dG adduct compared to control while a reverse trend was observed with AF-dG adduct. The addition of quencher enhanced the luminescence ratio between AF-modified and control duplex by 1.5 fold compared to 3.6 to 6-fold in AAF-dG adduct. The results from this study demonstrate the role of conformational heterogeneity of the arylamine-dG adduct in the binding of the Ru(II) complex and also provides us insight on the development of new probes.[Ru(phen)2(dppz)]2 + sensitizes the N-acetyl aminofluorene-deoxyguanosine(AAF-dG) better than aminofluorene-deoxyguanosine(AF-dG) adduct and the control.Display Omitted
Keywords: Arylamine; DNA adduct; Ru(II) complex; Acetylaminofluorene; Aminofluorene;

A cyclopalladated phosphine selenide with an anionic acylselenourea ligand by Anja Molter; Jörg Rust; Christian W. Lehmann; Fabian Mohr (69-71).
The chloro-bridged cyclometallated palladium(II) complex [PdCl{κC,Se-C6H4P(Se)Ph2}]2 reacts with 4-MeC6H4C(O)NHC(Se)NEt2 in the presence of base to give [Pd{κC,Se-C6H4P(Se)Ph2}{κO,Se-4-MeC6H4C(O)NC(Se)NEt2}] in high yield. The complex was fully characterised by spectroscopic methods and also X-ray diffraction. This compound represents one of the few examples of a metal complex containing two different selenium-containing ligands.The preparation and spectroscopic and structural characterisation of the palladium(II) complex [Pd{κC,Se-C6H4P(Se)Ph2}{κO,Se-4-MeC6H4C(O)NC(Se)NEt2}], featuring two different selenium-containing ligands is described.Display Omitted
Keywords: Selenium; Palladium; Cyclometallation; Phosphine selenide; Selenourea; X-ray structure;

Extractive complexation of lanthanides and Am(III) by 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone in ionic liquid: Solvent extraction and spectroscopic studies by Rajesh B. Gujar; Seraj A. Ansari; Arijit Sengupta; Mallekav S. Murali; Prasanta K. Mohapatra (72-76).
Extraction behaviour of trivalent actinides and lanthanides was studied using solutions of 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (HPMBP), a beta-diketone, in a room temperature ionic liquid, 1-methyl-3-octyl-imidazolium bis(trifluoromethylsulphonyl) imide (C8mim·Tf2N). The complex extracted into C8mim·Tf2N differs in its composition than those observed in molecular diluents such as benzene. Whereas, neutral ML3 complex is predominant in molecular diluents, a positively charged complex, [ML2·HL]+ (where M = La3 +, Eu3 +, Lu3 + and Am3 +; L = PMBP; HL = HPMBP), was identified to be extracted into the ionic liquid medium. Luminescence spectroscopic studies suggested presence of four inner-sphere water molecules in the extracted species. This paper reports for the first time the stability constant of a lanthanide (Nd3 +) complex with HPMBP in C8mim·Tf2N which are significantly larger than those reported in molecular diluents. Thermodynamic parameters were also determined to throw light on the nature of complexation.Extraction behaviour of trivalent actinides and lanthanides was studied using solutions of HPMBP in a room temperature ionic liquid and the nature of the extracted species was investigated by slope analysis, luminescence spectroscopy and thermodynamic studies. Complex formation constants with Nd3 + ions were reported for the first time.Display Omitted
Keywords: Lanthanides; Extraction; Complexation; Ionic liquid; Pyrazolone;

A solvent free nickle(II) compound derived from 5-(4-pyridyl)tetrazole-2-acetic acid for potential energetic material by Peng Peng Sun; Jia Fang Dong; Yun Wang; Yu Jie Liu; Fan Sun; Jun Wei Yuan; Gao Wen Yang; QiaoYun Li (77-79).
Coordination compounds based on tetrazole compounds may be potential candidates for energetic materials. A solvent free compound with three dimensional network [Ni(pytza)2]n was prepared from a solvothermal reaction by using Hpytza and Ni(ClO4)2·6H2O, where Hpytza = 5-(4-pyridyl)tetrazole-2-acetic acid. This compound was characterized by elemental analysis, IR and single crystal X-ray diffraction. Thermal behavior of the compound was characterized by differential scanning calorimetry (DSC) and thermogravimetric-differential thermogravimetric (TG-DTG). Furthermore, the apparent activation energy (E); Arrhenius equation; critical temperature (Tp); oxygen balance (OB %); entropy of activation (△S), enthalpy of activation (△H), and free energy of activation (△G) of the decomposition process were discussed, as well. This compound has a potential as energetic material.Display Omitted
Keywords: 5-(4-Pyridyl)tetrazole-2-acetic acid; Nickle(II); Crystal structure; Energetic material;

Visible-light-driven CO2 photo-catalytic reduction of Ru(II) and Ir(III) coordination complexes by Wei-Ming Liao; Jian-Hua Zhang; Ya-Jun Hou; Hai-Ping Wang; Mei Pan (80-89).
Photo-induced carbon dioxide conversion presents one of the basic reactions of natural photo-syntheses in green plants, which has inspired researchers to develop artificial materials and devices for efficient CO2 photo-reduction into useful products and chemical fuels via light-driven photochemical reactions. This review article focuses on recent advances in visible-light-driven CO2 photo-catalytic reduction studies based on Ru(II) and Ir(III) coordination complexes.

A luminescent two-fold interpenetrated pillared-layer metal-organic framework for highly selective and sensitive sensing of Fe3 + by Xian-Dong Zhu; Kun Zhang; Wei-Xiang Zhou; Qing-Hai Li; Ying-Qiang Fu; Rong-Mei Liu; Gui-Xiang Qian (90-93).
A luminescent three-dimensional metal-organic framework generally formulated as [Zn2(OH)(sip)(bpe)(H2O)]H2O (1), has been hydrothermally synthesized and characterized. It represents a new two-fold interpenetrated pillared-layer framework with (63)(69  · 8) topology constructed from π-electron-rich rigid ligand 5-sulfoisophthalic acid coupled with auxiliary ligand 1,2-bis(4-pyridyl)ethane. Interestingly, the strong emission of 1 could be quenched efficiently by trace amounts of Fe3 + at room temperature, even in the presence of other competing analogues, which indicated that 1 can serve as an excellent sensor for specific selective identification and quantification of Fe3 +.A new two-fold interpenetrated pillared-layer MOF has been hydrothermally synthesized and characterized. The luminescence study indicates that it is a promising material for specific selective identification and quantification of Fe3 +.Display Omitted
Keywords: Metal-organic framework; Aromatic sulfonic ligand; Interpenetrated pillared-layer structure; Luminescent sensor;

A 3D terbium-organic framework [TbK(BPDSDC)(DMF)(H2O)2]n (1) with the bifunctional carboxylate-sulfonate ligand of biphenyl-3,3′-disulfonyl-4,4′-dicarboxylate (BPDSDC4 −) was synthesized and characterized. The Tb3 + and K+ ions are briged by the carboxylate and sulfonate groups to give a 2D layer, which is linked by the biphenyl moieties to form the 3D pillared framework with the sulfonate groups pointing at the pores. The sulfonate groups on the pores act as the basic sites for the Cr3 + ion sensing by luminescence quenching, highlighting the potential for recognition of Cr3 + ion for compound 1 with the characteristic bright green color.A novel Tb-organic framework 1 based on the biphenyl-3,3′-disulfonyl-4,4′-dicarboxylate ligand has been synthesized. Compound 1 features a 3D pillared framework with the sulfonate sites pointing to the pores, which can capture the Cr3 +, highlighting the potential for Cr3 + ion luminescent sensor.Display Omitted
Keywords: Terbium compound; Biphenyl-3,3′-disulfonyl-4,4′-dicarboxylate; Cr3 + ion luminescent sensing;

Two novel coordination polymers, namely {[Ni2(dpb)(Hdpb)2(4,4′-bbibp)2(H2O)]·H2O} (1) and [Ni(dpb)(bimb)(H2O)] (2) (H2dpb = 3,5-di(4′-carboxyl-phenyl)benzene acid, 4,4′-bbibp = 4.4′-bis(benzoimidazo-1-ly)biphenyl, bimb = 1.4-bis(imidazol-1-ylmethyl)benzene) have been synthesized under hydrothermal conditions and characterized by elemental analysis, IR spectra, powder X-ray diffraction (PXRD), thermogravimetric (TG) analysis and single-crystal X-ray diffraction. Complex 1 shows a rare 1D meso-helical ladder chain, and the adjacent 1D irregular ladder chain forms a 3D supramolecular framework through the O―H ⋯ O and C―H ⋯ π interactions. Complex 2 exhibits an unprecedented 2-nodal (2,4)-connected 2D layer structure with the Schläfli point symbol (84  · 122)(82), which are further assembled into a 3D supramolecular structure also by O―H ⋯ O interactions. Furthermore, the photocatalytic properties of complexes 1 and 2 have been investigated. Interestingly, complex 2 not only shows an remarkable photocatalytic activity on RhB/MB degradation, but also has a better adsorption activity based on the bigger channel under magnetically stirred in the dark for 30 min.Two rare Ni(II) coordination polymers based on semi-rigid and rigid N-donor ligands were obtained. Their photocatalytic properties were investigated.Display Omitted
Keywords: Coordination polymer; Meso-helical ladder chain; Photocatalytic properties; Adsorption activity;

A two-fold interpenetrated metal-organic framework{[Zn(bpydb)(H2O)](DMF)0.75} (1, DMF =  N,N-dimethylformamide), involving the aromatic trigonal heterofunctional ligand 4,4′-(4,4′-bipyridine-2,6-diyl) dibenzoic acid (bpydbH2) and Zn(II) metal center has been successfully synthesized under solvothermal condition. The structure of 1 was characterized by single-crystal X-ray diffraction, which shows a two-fold interpenetrated 3-connected framework with ThSi 2 -type topology. The luminescent sensing of different nitro-explosives was investigated, and the results indicated that 1 could behave as an effective sensor for detecting picric acid (PA) with high selectivity and sensitivity. Furthermore, the quenching mechanism has also been investigated in detail.A new 3D Zn-based luminescence metal–organic framework with two-fold interpenetrated net consisting of a 3D ThSi 2 -type topology has been successfully synthesized. This compound could behave as an effective sensor for detecting picric acid (PA) with high selectivity and sensitivity among the nitro-explosives studied. Furthermore, the quenching mechanism has also been investigated in detail.Display Omitted
Keywords: Zn-MOF; ThSi2-type topology; Luminescence properties; Selective detection;

Syntheses, crystal structures and properties of self-assembly supramolecular compound based on cucurbit[6]uril by Guoshuai Zhang; Yuekun Zhang; Weibo Ren; Jinpeng Liu; Mei Liu (107-110).
A new cucurbit [6]uril based compound {[Cd2Cl2(INA)2(HCOO)2(H2O)2](CB [6])·2(HCOOH)·5H2O}(CCUT-101) was synthesized by the solvothermal reaction of cadmium chloride, cucurbit[6]uril (CB[6]), and isonicotinic acid (HINA). X-ray diffraction analysis indicated that coordination of INA with the Cd2 + resulted in the formation of some one-dimensional wave-like chains, which connected with CB[6] by π ⋯ π stacking and hydrogen bonding, and further extended to a 2D layer. The luminescence behaviors and sensing properties of CCUT-101 in different solvents were carried out.A novel cucurbit[6]uril-based compound was synthesized by the solvothermal reaction in the presence of INA as a structure-directing agent. The luminescence properties of CCUT-101 in different solvent emulsions were investigated. The luminescence changes in different solvent emulsions suggested that it is possible to sense different solvents.Display Omitted
Keywords: Cucurbit[6]uril; Solvothermal; Supramolecular interactions; Sensing property;

Phase transition and thermal expansion of Ho2W3O12 by Weigang Cao; He Zhu; Zhanning Liu; Jinxia Deng; Jun Chen; Xianran Xing (111-114).
The phase formation of Ho2W3O12 is still in debate, and no detailed analysis was carried out until now. In the present study, we synthesized Ho2W3O12 with different treatments to probe the relationship between phase formation and synthesized conditions. It is found that the orthorhombic phase of Ho2W3O12 is stable at high temperature. While the thermodynamic stable phase of low temperature is monoclinic. The temperature of phase transition was determined at 908 °C. Moreover, the phase transition is slow, so it is easy to retain the orthorhombic phase at low temperature. Additionally, the stability and the thermal expansion of orthorhombic Ho2W3O12 were also investigated. The orthorhombic phase can be stabilized by 600 °C, and shows negative thermal expansion (NTE) along three axes with the overall volume thermal contraction of − 2.1 × 10− 5  °C− 1.Orthorhombic Ho2W3O12 shows NTE (− 2.1 × 10− 5  °C− 1) in the temperature range of 200–600 °C.Display Omitted
Keywords: Ho2W3O12; Cooling rate; Phase transition; Negative thermal expansion (NTE);

A couple of Co(II) enantiomers constructed from semirigid lactic acid derivatives by Zhong-Xuan Xu; Yu-Lu Ma; Li-Shuang Zhang; Jian Zhang (115-118).
Enantiopure organic linkers (R)-H2CBA and (S)-H2CBA have been synthesized from nature lactic acid and rigid 4-hydroxybenzoate. With the help of auxiliary ligand 4,4′-BIP, (R)-H2CBA and (S)-H2CBA afford two enantiomeric coordination polymers, namely [Co2((R)-CBA)2(4,4′-BIP)2]⋅ xH2O (1-D) and [Co2((S)-CBA)2 (4,4′-BIP)2]⋅ xH2O (1-L). In complexes 1-D and 1-L, the CBA2 − ligands and dinuclear Co units form 4-connected Co-CBA layers, which are further linked to a pillared-layer framework with 2-fold interpenetration pcu structure by 4,4′-BIP ligands. Moreover, complex 1-D displays antiferromagnetic interactions.A pair of semirigid organic ligands integrating benzoic acid and lactate units have been synthesized and employed to the construction of enantiomeric coordination polymers.Display Omitted
Keywords: Semirigid lactic acid derivatives; Enantiomeric coordination polymers; 2-Fold interpenetration structure; Antiferromagnetic interactions;

Two new extended Preyssler-type polyoxometalates (POMs) constructed by Fe(III), 2,2′–biimidazole and Preyssler–type tungstophosphate anions with Na and Ag cavity centers respectively, namely {(H4biim)5H[Fe(H2biim)(H2O)2(ZP5W30O110)]·17H2O}n (Z = Na, compound 1; Z = Ag, compound 2; H2biim = 2,2′–biimidazole), were designed and synthesized under hydrothermal conditions, and were systematically characterized by physico–chemical and spectroscopic methods. The two compounds are isostructural coordination polymers. In compound 1 or 2, there exists interesting infinite 1D chains composed of Preyssler–type [ZP5W30O110]14− (abbreviated as {ZP5W30}) polyanions bridged by Fe(III)–complex fragments, and these chains further formed 3D supramolecular frameworks via extensive hydrogen–bonding interactions. Especially for compound 2, two types of transition metals, i.e. one Ag+ ion as a center in the inner cavity and two Fe3+ ions as modified cations on the outer surface of one {ZP5W30} unit, existed in the same compound. Additionally, the electrochemical behaviors and acid catalytic activities of compounds 1 and 2 have been investigated.Two new extended Preyssler-type polyoxometalates with different cavity centers constructed by Fe(III), 2,2′–biimidazole and Preyssler–type tungstophosphate anions display higher catalytic performances toward the synthesis of cyclohexanone ethylene ketal and can be reused.Display Omitted
Keywords: Preyssler–type polyoxometalate; Tungstophosphate; Iron (III)–complex; Hydrothermal synthesis; Acid catalysis;

Studies on interaction of Cr(III) polypyridyl complexes with DNA by B. Babu; T. Nandhini; V.G. Vaidyanathan; Balachandran Unni Nair (124-128).
Two chromium(III) complexes containing derivatives of 1,10-phenanthroline were synthesized and characterized using different spectroscopic methods. The interaction of the synthesized complexes with DNA was performed. From the absorption titration data, the binding constant for the complexes [Cr(imiphen)2Cl2]+ (1) and [Cr(furphen)2Cl2]+ (2) with DNA were found to be 5.69 ± 0.3 × 104  M− 1 for 1 and 3.7 ± 0.2 × 104  M− 1 for 2, respectively. The viscosity studies show that both the complexes bind to DNA in a partial intercalative mode. The results of competitive binding assay reveal that both complexes displace EB from DNA marginally. Gel electrophoresis data show that both the complexes 1 and 2 requires co-reagent to induce DNA cleavage but complex 2 exhibit better nuclease activity compared to complex 1. The results from this study describe the role of ligand structure in the binding and cleavage of DNA as furan based ligand exhibit better cleaving ability compared to imidazole moiety.Results show that complex 2 exhibit better nuclease activity compared to complex 1 in the presence of coreagent.Display Omitted
Keywords: Chromium(III); Polypyridyl; DNA; Viscosity; Competitive binding assay; Nuclease activity;

A cerium-based metal-organic tetrahedron for fluorescent recognition of 5-HIAA and its application in urine test by Yang Jiao; Hai-yang He; Ji-qiu Yin; Lu Zhou; Cheng He; Chun-ying Duan (129-133).
A cerium-based metal-organic tetrahedron including triphenylamine was applied to recognize the 5-hydroxyindole-3-acetic acid (5-HIAA), a kind of tumor marker and playing crucial roles in the process of the disease diagnosis and clinical treatment. The tetrahedron could encapsulate 5-HIAA through weak interaction and space stereoselectivity, and it displayed good fluorescence enhancement towards 5-HIAA over other relevant species in urine. The tetrahedral sensor is capable of detecting 5-HIAA with good selectivity and high sensitivity in real urine.The tetrahedron exhibited sensitivity and good selectivity for 5-HIAA over other biologically relevant species in urine, and it could encapsulate 5-HIAA through weak interaction and space stereo selectivity.Display Omitted
Keywords: Urine test; Tumor marker; Fluorescent sensor;

Synthesis, structure and photocatalytic properties of an unusual tetranuclear copper(II) coordination polymer by Shan Zhao; Ya-Qian Zhang; Tian-Rui Zheng; Lu-Lu Shi; Bao-Long Li; Yong Zhang (134-137).
An unusual coordination polymer [Cu4(OH)2(otrb)2(sip)2]n (1) was synthesized by the hydrothermal method (otrb = 1,2-bis(1,2,4-triazol-4-ylmethyl)benzene, sip = 5-sulfoisophthalate). The tetranuclear copper(II) clusters [Cu4(OH)2] are bridged by the double sip and double otrb ligands to form an unusual 2D sql network. The adjacent 2D networks parallel interpenetrate each other to form intriguing 2-fold interpenetrated network. The photocatalytic degradation rates of methyl orange (MO), methylene blue (MB) and rhodamine B (RhB) are 94.4%, 91.2% and 86.6% at 180 min using photocatalyst 1. 1 is a highly efficient and universal photocatalyst for the degradation of the organic dyes.An unusual coordination polymer with 2-fold interpenetrated 2D sql network based on tetranuclear copper(II) clusters [Cu4(OH)2] is a highly efficient and universal photocatalyst for the degradation of the organic dyes.Display Omitted
Keywords: Tetranuclear copper(II) cluster; Coordination polymer; Structure; Photocatalysis; Bis(triazole);

Potential anti-cancer activity of a novel Bi(III) containing thiosemicarbazone derivative by Ruizhuo Ouyang; Yang Yang; Xiao Tong; Yaoqin Yang; Huihong Tao; Tianyu Zong; Kai Feng; Pengpeng Jia; Penghui Cao; Ning Guo; Haizhou Chang; Shuang Zhou; Yuqing Miao (138-141).
By mixing 5-bromo-2-furaldehyde, phenylthiosemicarbazide and Bi(CH3COO)3, a new amorphous bismuth-containing complex, BiL2Cl3, was synthesized under aqueous conditions via a one-pot method and characterized with some analytical techniques, where L was produced by dehydration between 5-bromo-2-furaldehyde, phenylthiosemicarbazide. The obtained complex effectively inhibited the proliferation and migration of A549 and H460 lung cancer cells, induced cell apoptosis and displayed fairly low cytotoxicity to normal human lung fibroblast (HLF). Compared with cisplatin, BiL2Cl3 displayed better anti-cancer activity against tumor cells and lower toxicity to normal cell. Therefore, BiL2Cl3 with potent anti-cancer activity may be a viable drug candidate in anti-cancer therapies.By mixing 5-bromo-2-furaldehyde, phenylthiosemicarbazide and Bi(CH3COO)3, a new amorphous bismuth-containing complex was synthesized under aqueous conditions via a one-pot method, which effectively inhibited the proliferation and migration of A549 and H460 lung cancer cells, induced cell apoptosis and displayed fairly low cytotoxicity to normal human lung fibroblast (HLF), indicative of great potential anti-cancer activity.Display Omitted
Keywords: Bi(III) complex; Thiosemicarbazone derivative; Anti-cancer ability; Lung cancer; A549 and H460;

Octanuclear zinc(II) carboxylate framework based on 1,4-naphthalenedicarboxylic acid by Binfang Meng; Yuqi Liu; Yubo Xing; Xinying Wang; Wei Li (142-146).
A novel Zn(II)-cluster-based coordination polymer-namely, {[Zn84-O)2(1,4-ndc)6(DMF)3]⋅ DMF}n (1) was synthesized using Zn(NO3)2 with 1,4-naphthalenedicarboxylic acid (1,4-H2ndc) under solvothermal conditions using CH3OH/H2O/DMF (6:1:1) as solvents and characterized by single crystal X-ray diffraction, elemental analysis, thermogravimetric analysis, and luminescent measurements. The complex 1 features a 3D structure based on the octanuclear metal cluster of [Zn84-O)2(OOCR)12(DMF)3] as secondary building unit, which possesses a (412  · 63) network topology considering the octanuclear cluster as 6-connected nodes. Thermal property and photoluminescence investigations revealed that the complex 1 displays a high thermal stability, and a strong emission spectrum peak at 403 nm at room temperature, and the complex 1 may be a technically viable option for the luminescence materials.A novel coordination polymer has been synthesized by self-assembly of zinc with varied polycarboxylates (1,4-naphthalenedicarboxylic acid) and N,N-dimethylformamide, which present 3D structure based on [Zn84-O)2(COO)12] octanuclear as secondary building unit.Display Omitted
Keywords: Crystal structure; Octanuclear cluster; Photoluminescent; zinc(II) complex; 1,4-Naphthalenedicarboxylic acid;

A highly selective turn-on sensor for Hg2 + based on a phosphorescent iridium (III) complex by Qunbo Mei; Yujie Shi; Chen Chen; Qingfang Hua; Bihai Tong (147-151).
A highly selective phosphorescent chemosensor for Hg2 + based on the iridium (III) complex Ir(DTBT)2(acac) (DTBT = 2-(5-(1,2 dihydroacenaphthylen-5-yl)thiophen-2-yl)benzothiazole, acac = acetylacetone) was synthesized and characterized. Ir(DTBT)2(acac) exhibited relatively weak fluorescenceat at about 700 nm. Ir(DTBT)2(acac) displayed a dramatic color change from near-infrared to yellow-green with the addition of Hg2 +. More significantly, the chemosensor performed “turn-on” phosphorescent responses toward Hg2 +.A highly selective phosphorescent chemosensor for Hg2 + based on the iridium (III) complex Ir(DTBT)2(acac) (DTBT = 2-(5-(1,2 dihydroacenaphthylen-5-yl)thiophen-2-yl)benzothiazole, acac = acetylacetone) was synthesized and characterized. Ir(DTBT)2(acac) exhibited relatively weak fluorescenceat at about 700 nm. Ir(DTBT)2(acac) displayed a dramatic color change from near-infrared to yellow-green with the addition of Hg2 +. More significantly, the chemosensor performed “turn-on” phosphorescent responses toward Hg2 +.Display Omitted
Keywords: Iridium (III) complex; Benzothiazole derivatives.; Phosphorescent chemosensor; Hg2 +;

Two new inorganic–organic hybrid complexes derived from polyoxovanadate and different bis-pyridyl-bis-amide ligands, (3-dpye =  N,N′-bis(3-pyridinecarboxamide)-1,2-ethane, 4-dpye =  N,N′-bis(4-pyridinecarboxamide)-1,2-ethane): [V2O6Zn(4-dpye)]n (1) and {[Zn(3-Hdpye)(H2O)5]2[V10O28]}·4H2O (2), have been hydrothermally prepared. In complex 1, the [V4O12]4 − clusters were connected by ZnII ions to generate a 2D inorganic layer, which is further linked by the μ 2-bridging 4-dpye ligands to form a 3D metal-organic framework. In complex 2, the [V10O28]6 − clusters connect with discrete zinc cation complex [Zn(3-Hdpye)(H2O)5]3 + through hydrogen bonds to generate a 2D supramolecular network. The N-donor position of organic ligands and V2O5 raw materials show great effect on the final structures. The fluorescence properties and the photocatalytic activities of the title complexes have been investigated.Two new inorganic–organic hybrid complexes derived from polyoxovanadate and different bis-pyridyl-bis-amide ligands have been prepared. Their fluorescence properties and photocatalytic activities have been discussed.Display Omitted
Keywords: Polyoxovanadate; Bis-pyridyl-bis-amide; Crystal structure; Fluorescence; Photocatalytic properties;

Two types of anion water clusters have been observed in cucurbit[6]uril based pseudorotaxanes with two kinds of guests. (COO)2(C2H5OH)2(H2O)4 anion water clusters and (H2O)2 water clusters are formed with the carboxylate groups of the guest 1, 1′-(hexane-1, 6-diyl) dipyridinium-4-carboxylate inner salt (HDPC) and connect the pseudorotaxane molecules to form 3D networks. Anion water clusters Cl2 (H2O) with independent water molecules are observed in the crystal structure of the pseudorotaxane with the guest 1, 1′-(hexane-1, 6-diyl) dipyridinium-4-hydroximic acid dichloride (HDHD). The results revealed that terminal groups of the guests, the solvents and the anions species in cucurbit Arunachalam and Ghosh (2011) uril pseudorotaxanes could affect the structures and the sizes of water clusters.The structures and sizes of anion water clusters in pseudorotaxanes are influenced by solvent and the terminal groups of the guests.Display Omitted
Keywords: Water clusters; Cucurbituril; Pseudopolyrotaxane; Self-assemble; Hydrogen bonds;

Three metal–organic networks, namely, [Zn2(Hnip)(4-bpdb)(nip)2(μ 3-OH)] (1), {[Zn(tbip)(4-bpdb)1.5]·CH3OH}n (2), and {[Ni(1,3-bdc)(4-bpdb)]·2H2O}n (3) (4-bpdb = 1.4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene, H2nip = 5-nitroisophthalic acid, H2tbip = 5-tert-butylisophthalic acid, and 1,3-H2bdc = 1,3-benzenedicarboxylic acid) are synthesized under hydrothermal conditions. The structure of 1 is built around uncommon rhombic {Zn4} clusters with double T d and double O h Zn(II) geometries, which extend into a 2D network by the rigid deprotonated H2nip and 4-bpdb bridges. Meanwhile, 2 presents a novel 2D → 3D parallel polycatenated framework assembled from 2D bilayers with cuboids as the fundamental building units. Compound 3 features an interesting 2D → 3D inclined polycatenated network based on 44-sql subunits. Moreover, the thermal stabilities, photoluminescence, and magnetic properties of the compounds are also discussed.Three coordination polymers are reported: compound 1 exhibit a 2D network with rhombic {Zn4} clusters, while 2 and 3 possess a parallel and a inclined 2D → 3D polycatenated framework, respectively.Display Omitted
Keywords: Bis-pyridyl ligand; Coordination polymer; Crystal structure; Magnetic property; Polycatenated framework;

Construction of a mixed-valence Mn16 cluster with four tetrahedrons by Feng Wang; Zhengbing Fu; Liangui Guo; Jun Du; Yu Ding (166-169).
The synthesis, crystal structure, and magnetochemical properties of a mixed-valence Mn16 cluster are reported. The compound contains a Mn162-O)23-O)24-O)6 core, which is constructed from four tetrahedrons. Magnetic susceptibility measurements indicate the presence of dominant antiferromagnetic exchange interaction within the compound.A mixed-valence Mn16 cluster contains the Mn162-O)23-O)24-O)6 core. Magnetic susceptibility measurements indicate the presence of dominant antiferromagnetic exchange interaction within the compound.Display Omitted
Keywords: Benzimidazole alkoxide ligand; Polynuclear manganese cluster; Crystal structure; Magnetic properties;

A luminescent europium metal-organic framework[Eu(Hbptc)(H2O)3]n (1) has been successfully prepared by the facile hydrothermal reaction of Eu(NO3)3  ⋅ 6H2O and the π-conjugated ligand H4bptc (H4bptc = biphenyl-2,3,3′,5′-tetracarboxylic acid). Single crystal structure analysis reveals that 1 exhibits a 2D layered structure. The luminescence studies revealed that this material can be selectively and sensitively quenched or enhanced by some small organic molecule solvents, showing potential as fluorescence probe.A highly luminescent 2D Eu-MOF was designed and successfully synthesized. Eu-MOF can sense some organic small molecules based on luminescence quenching effect. Interestingly, the visible red emission of Eu-MOF could be quantitatively quenched upon the addition of phenylamine at low concentrations.Display Omitted
Keywords: Metal-organic framework; Luminescence; Selective sensing; Small organic molecule;

A bibliometric analysis based on the Science Citation Index Expanded from Web of Science was studied for research activities of the global metal-organic frameworks (MOFs) from 1995 to 2014. Study emphases included document types, languages, performance of publication covering annual outputs, journals, Web of Science categories, countries, and institutions. Six publication indicators including total, independent, collaborative, first authored, and corresponding authored, and single authored publications were used to evaluate publications of countries. China took a leading position of 75 countries while articles published by the USA had higher impact. An indicator SIN, a proportion of single institution articles:internationally collaborative articles:nationally collaborative articles (S:I:N) was applied to compare and describe institutions' publication characteristics. Based on number of citations since papers published to the end of the last year, citations per publication and h-index for highly cited articles were compared. In addition, Yaghi's group published the first article in the MOFs field and they contributed eight of the top ten leading articles in 2014.Publications of the seven most productive countries during 1991–2014.Article lives of the top ten articles (C 2014  > 140).Display Omitted
Keywords: MOFs; SCI-EXPANDED; Scientometrics; Citations; Indicators;

Two flexible V-shaped dicarboxylate coligands (H2IBG = isophthaloylbisglycine, and H2PPDA = 4,4′-(perfluoropropane-2,2-diyl)dibenzoic acid) were selected to construct two new amino-functionalized coordination polymers based on Zn salt and a rigid linear ligand L (L = 3,6-di(3-imidazolyl)benzene-1,2-diamine. Both {[Zn(PPDA)(L)]·3H2O}n (1) and {[Zn2(IBG)(L)]·2H2O}n (2) were crystallized in mononuclear structure. Complex 1 shows a 3-D super structure based on ABAB packing, while complex 2 shows a 2-D layered structure. Structural diversity was acquired due to the flexibility of dicarboxylate ligands. Crystallographic and spectroscopic properties of both complexes were explored.Display Omitted
Keywords: Coordination polymer; Crystal structure; Amino-functionalized; Zn(II) compound;

A new organic-inorganic hybrid dimeric hexaniobate linked by Co-complex by Shufang Zhao; Zhijie Liang; Lanying Song; Pengtao Ma; Dongdi Zhang; Jingping Wang (187-189).
A new organic-inorganic polyoxoniobate KNa[Co(en)3]2[(HNb6O19)Co(en)]2·30H2O (1) has been successfully synthesized under hydrothermal condition which has been characterized by single-crystal X-ray diffraction, IR spectrum, thermogravimetric analysis and X-ray photoelectron spectroscopy. Compound 1 crystallizes in Ibam space group with a  = 19.0985(8) Å, V  = 27581(2) Å3, Z  = 8. X-ray structure analysis reveals that the title polyanion consists of a dimeric alignment constructed from two Lindqvist-type {Nb6O19} subunits via two {CoIII(en)} connectors.Compound 1 was obtained by the reaction of K7HNb6O19·13H2O with CoCl2·6H2O and en using hydrothermal method and the polyanion 1a consists of a dimeric alignment constructed from two Lindqvist-type {Nb6O19} subunits via two {CoIII(en)} connectors.Display Omitted
Keywords: Crystal structure; Organic-inorganic hybrid; Polyoxoniobate;

Two isostructural 3D europium metal–organic frameworks incorporating similar Eu-fluorine substituted carboxylate tectonics, {[Eu4(Mimda)4 (Tfpa)2·4H2O]}n (1) and {[Eu4(Pimda)4 (Tfpa)2·4H2O]}n (2) (Mimda = 2-methyl-1H-imidazole - 4, 5–dicarboxy acid, while Pimda = 2-propyl-1H-imidazole - 4, 5–dicarboxy acid and Tfpa = (3,4,5,6-tetrafluoro-1,2 phthalate acid) have been synthesized under the hydrothermal conditions. They have been systematically characterized by elemental analyses, IR spectra and PXRD patterns. Single crystal X-ray diffraction analysis reveals that each polymer possesses infinite rod-shaped chain consist of dinuclear Eu-carboxylate building units, which are further pillared by imidazole-dicarboxylate ligands to give rise to 3D open non-interpenetrated frameworks, featuring a (6, 4)-connected pseudo-primitive cubic (pcu) topology. Both two polymers exhibit efficiently sensitized red luminescence due to an energy transfer from substituted dicarboxylate ligand to Eu(III) ions in solid state. Polymer 1 also demonstrates tunable or switchable fluorescence signals in response to the different solvents. Moreover, the luminescent intensity of 1 is increased linearly with the increasing concentration of Pb2 + cation in N,N-dimethyl formamide (DMF) suspension, while shows declining trend with Cd2 + cation being introduced.Two isostructural 3D europium metal–organic frameworks incorporating similar Eu-fluorine substituted carboxylate moieties have been synthesized under hydrothermal conditions. Each polymer possesses the open 3D non-interpenetrated frameworks featuring a (6, 4)-connected pseudo-primitive cubic (pcu) topology. It also demonstrates tunable or switchable fluorescence signals in response to the different solvates. The luminescent intensity of 1 is increased linear with the increasing concentration of Pb2 + cation in N,N-dimethyl formamide (DMF) suspension, and polymer 1 may be employed as a fluorescence ratiometric probe for pollutant cations.Display Omitted
Keywords: Europium coordination polymer; Fluorine substituted carboxylic acid; Pollutant cations detecting; Thermogravimetry analysis;