Inorganic Chemistry Communications (v.49, #C)

Contents List (iii-xii).

Synthesis and properties of fullerene (C60) substituted cyclophosphazene derivatives by Elif Okutan; Bünyemin Çoşut; Serkan Yeşilot (1-4).
A series of fullerene (C60) substituted cyclophosphazene derivatives (2a–4a) were synthesized for the first time by 1,3-dipolar cycloaddition of the 1-formylphenoxy (aryloxy)cyclotriphosphazenes (2–4) (aryloxy = phenoxy, 1-naphthoxy and 1-pyrenoxy) and C60. All the obtained compounds were characterized by 1H NMR, 13C NMR, 31P NMR, UV–Vis, fluorescence spectroscopy, MALDI-TOF and elemental analysis. The thermal behaviors of the synthesized compounds were investigated by Thermal Gravimetric Analysis (TGA).A series of C60–cyclophosphazene derivatives were synthesized and characterized. Photophysical and thermal behaviors of these molecules were investigated by UV–Vis, fluorescence and TGA measurements.Display Omitted
Keywords: Cyclotriphosphazene; Fullerene; NMR; Fluorescence;

The reaction of trans-[ReOBr3(PPh3)2] with 5-amino-orotic acid (H2aoa) in ethanol led to the isolation of the triply-bridged dimer [ReIV 2(μ-O)(μ-Br)(μ-aoa)Br(OEt)2(PPh3)2] (1). The compound has a ReRe bond distance of 2.5526(4) Å. The dianionic bridging ligand aoa coordinates bidentately via an amido nitrogen and carboxylate oxygen to one Re ion, and monodentately through a neutral carbonylic oxygen to the second metal ion. Density functional theory (DFT) calculation shows that the presence of the rhenium atoms leads to a noncollinear spin phase arrangement for the bridging atoms.The reaction of trans-[ReOBr3(PPh3)2] with 5-amino-orotic acid (H2aoa) in ethanol led to the isolation of the triply-bridged dimer [ReIV 2(μ-O)(μ-Br)(μ-aoa)Br(OEt)2(PPh3)2]. The compound has a ReRe triple bond distance of 2.5526(4) Å. The dianionic bridging ligand aoa coordinates bidentately via an amido nitrogen and carboxylate oxygen to one Re ion, and monodentately through a neutral carbonylic oxygen to the second metal ion.Display Omitted
Keywords: Rhenium (IV); Orotic acid; Chelate-bridged; Triple bond; DFT; Noncollinear spin;

The first crystallographically-characterised Cu(II) xanthate by Andrew L. Johnson; Michael S. Hill; Gabriele Kociok-Köhn; Kieran C. Molloy; Anna L. Sudlow (8-11).
The copper(II) xanthate Cu(S2COEt)2·TMEDA (1) (TMEDA =  N,N-tetramethylethylenediamine) has been synthesised and is the first structurally-characterised xanthate of copper in the + 2 oxidation state. 1 has an octahedral cis, cis, cis-ligand arrangement about the metal, in which xanthate chelation is markedly asymmetric. Both bulk thermal decomposition and film growth by aerosol-assisted chemical vapour deposition (AACVD) using 1 as precursor lead to the formation of Cu2S.
Keywords: Copper; Xanthate; Adduct; X-ray crystallography; AACVD;

Extended architecture formed by linkage of a new type of decamolybdate {Mo10O34} unit and Cu3 cluster by Yonghong Yan; Bin Liu; Chengxin Yu; Xiaofen Zhang; Huaiming Hu; Ganglin Xue (12-15).
A novel extended architecture based on unprecedented decamolybdate unit and Cu3 cluster, (NH4)2n [Cu3(atrz)6Mo10O34] n (1) (atrz = 4H-4-amino-1,2,4-triazole), has been synthesized under the hydrothermal conditions. The decamolybdate unit in 1 represents an unprecedented type {Mo10O34} skeleton and is composed of γ-octamolybdate subunit capped two {MoO6} octahedra at corners by sharing three oxygen atoms. The capped {MoO6} octahedra of decamolybdates and the external copper ions of the linear trinuclear cation [Cu3(atrz)6]6 + further connect alternately to form a 1D chain. Magnetic measurement reveals the antiferromagnetic interactions among the Cu3 cluster.A novel extended inorganic–organic hybrids based on unprecedented isopolymolybdate unit and Cu3 cluster has been successfully synthesized and fully characterized.Display Omitted
Keywords: Polyoxometalates; Cluster; Polynuclear; Magnetic properties;

A thermally stable dysprosium porphyrin with a three-dimensional (3D) porous open framework, [Dy(H2TPPS)] n ∙  nH3O∙2nH2O (1) (H2TPPS = tetra(4-sulfonatophenyl)porphyrin), has been synthesized via hydrothermal reactions and structurally analyzed by an X-ray single-crystal diffraction method. The 24-membered macrocyclic ring of H2TPPS is exactly coplanar and the center is free from metal. The dysprosium ion is coordinated by eight Osulfonic atoms from eight H2TPPS moieties, forming a distorted square anti-prism geometry. Complex 1 shows a void space of 210 Å3, occupying 9.06% of the unit-cell volume. The 3D porous open framework of 1 is thermally stable up to 380 °C. Complex 1 exhibits a red fluorescence emission with a quantum yield and lifetime of 2.7% and 136 μs, respectively. CV result reveals one reductive peak at − 0.33 V and one quasi-reversible wave with E 1/2  = − 0.81 V.A dysprosium porphyrin featuring a robust 3D porous open framework has been prepared. It is highly thermally stable. It displays a red fluorescence emission.Display Omitted
Keywords: Dysprosium; Hydrothermal; Open framework; Porphyrin; Thermally stable;

A new 3D Cu(II) coordination polymer [Cu2(4-dpna)2(2,5-tdca)2] (1) (4-dpna =  N 1,N 4-di(pyridin-4-yl)naphthalene-1,4-dicarboxamide, 2,5-H2tdca = thiophene-2,5-dicarboxylic acid) has been hydrothermally synthesized. Complex 1 is a novel 3D metal–organic coordination complex based on a semi-rigid naphthalene-based bis-pyridyl-bis-amide ligand, which shows a 3-fold interpenetrating network with a CdSO4-like topology. Moreover, the fluorescent property, electrochemical behavior and selective photocatalytic activity of 1 have been investigated.A 3-fold interpenetrating 3D framework with a 4-connected CdSO4-like topology was obtained, which represents the first example of coordination polymers with the semi-rigid naphthalene-based bis-pyridyl-bis-amide ligand and shows excellent photocatalytic activity and selectivity for the decomposition of RhB.Display Omitted
Keywords: Coordination polymer; Interpenetrating network; Semi-rigid bis-pyridyl-bis-amide ligand; Fluorescent property; Selective photocatalysis;

Dimeric ruthenium-triazolopyrimidine complex: Synthesis and structural characterization by Iwona Łakomska; Marzena Fandzloch; Andrzej Wojtczak (24-26).
Rare diruthenium(II) complex with the bridging 1,2,4-triazolo‐[1,5-a]pyrimidine (tp) ligand was synthesized and characterized using various analytical tools (X-ray crystallography, IR and 1H, 13C, 15N NMR). Assays of in vitro cytotoxicity against two human cancer cell lines (A549 — non-small cell lung carcinoma and T47D — breast carcinoma) and normal mice fibroblasts (BALB/3T3) have been carried out.Diruthenium(II) complex with the bridging 1,2,4-triazolo[1,5-a]pyrimidine (tp) ligand, of formulae [Ru2Cl22-Cl2)(dmso)2(μ-tp)]·H2O, was synthesized and characterized using various analytical tools (X-ray crystallography, IR and H, 13C, 15N NMR). Assays of in vitro cytotoxicity against two human cancer cell lines (A549 — non-small cell lung carcinoma and T47D — breast carcinoma) and normal mice fibroblasts (BALB/3T3) have been carried out.Display Omitted
Keywords: Dimeric ruthenium complex; Triazolopyrimidine; X-ray; 15N NMR;

N-heterocyclic carbene copper complexes tethered to iron carbidocarbonyl clusters by Roberto Della Pergola; Annalisa Sironi; André Rosehr; Valentina Colombo; Angelo Sironi (27-29).
The reactions of [Fe4C(CO)12(CuNCMe)x]x − 2 (x = 1, 2) with Im i Pr·HBF4 (Im i Pr = N,N′-bis(isopropyl)imidazol-2-ylidene) in the presence of NaH yielded [Fe4C(CO)12(CuIm i Pr)x]x − 2. The hetero-substituted [Fe4C(CO)12(CuCl)(CuIm i Pr)] was obtained by the deprotonation of the corresponding chloride salt. All products have been characterized by elemental analysis, NMR and single crystal X-ray diffraction analyses.Exploiting the lability of the copper sites, [Fe4C(CO)12(CuNCMe)x] clusters (x = 1, 2) can be substituted with N-heterocyclic carbene ligands, and the products can be structurally characterized. The Cu–Cu edge of [Fe4C(CO)12(Cu-NHC)2] is elongated to 3.06 Å to accommodate two such bulky ligands.Display Omitted
Keywords: Iron; Copper; Heterometallic clusters; NHC ligands; Interstitial carbide; Crystal structure;

Near-infrared (NIR) luminescent PMMA-based hybrid materials doped with Ln-β-diketonate (Ln = Nd or Yb) complexes by Chao Yu; Zhao Zhang; Lin Liu; Weixu Feng; Xingqiang Lü; Wai-Kwok Wong; Richard A. Jones (30-33).
Based on [Ln(L)3(H2O)2] (Ln = Nd, Yb or Er) complexes self-assembled from a trifluorinated acylpyrazole-type β-diketonate ligand HL ((Z)-3-methyl-1-phenyl-4-(2,2,2-trifluoro-1-hydroxyethylidene)-1H-pyrazol-5(4H)-one) and LnCl3·6H2O, a series of NIR luminescent PMMA-supported hybrid materials PMMA@[Ln(L)3(H2O)2] are obtained from physical doping. The immobilization of the luminescent species via physical and chemical interactions within the polymeric PMMA matrix also acting as co-sensitizer, endows the enhanced NIR luminescent properties (Φem  = 0.85–0.97%) in comparison to the individual Ln3 +-β-diketonate complex (Φem  = 0.53–0.79%) besides the improved thermal-stability properties.In the obtained PMMA-supported hybrid materials PMMA@[Ln(L)3(H2O)2] (Ln = Nd, Yb or Er), the immobilization of [Ln(L)3(H2O)2] luminescent species via physical and chemical interactions within polymeric PMMA matrix also acting as the co-sensitizer, endows the enhanced NIR luminescent properties (Φem  = 0.85–0.97%) in comparison to the individual Ln3 +-β-diketonate complex (Φem  = 0.53–0.79%) besides the improved thermal-stability and mechanical properties.Display Omitted
Keywords: NIR luminescence; PMMA-supported doping hybrid materials; Trifluorinated acylpyrazole-type β-diketonate; Lanthanides;

A new organic ligand of 1,2,4,5-tetrakis(3-carboxyphenyl)-benzene (m-H4TCPB) and its first metal–organic framework 1 [Cu2(m-TCPB)(H2O)2]n·[(DEF)3]n (DEF = N, N′-diethylformamide) was designed and synthesized. 1 has a three-dimensional (4,4) framework topology. The activated 1a exhibits permanent porosity and demonstrates selective toward adsorption of hydrogen over nitrogen at 77 K, and acetylene and carbon dioxide over methane at room temperature.A new organic ligand of 1,2,4,5-tetrakis(3-carboxyphenyl)-benzene (m-H4TCPB) and its first metal–organic framework 1 [Cu2(m-TCPB)(H2O)2]n·[(DEF)3]n (DEF = N, N′-diethylformamide) was designed and synthesized. 1 has a three-dimensional (4,4) framework topology. The activated 1a exhibits permanent porosity and demonstrates selective toward adsorption of hydrogen over nitrogen at 77 K, and acetylene and carbon dioxide over methane at room temperature.Display Omitted
Keywords: Metal–organic frameworks; 1,2,4,5-Tetrakis (3-carboxyphenyl)-benzene (m-H4TCPB); Gas separation; Selectivity; Virial method;

Synthesis and structure of a heterotrimetallic (Li/Er/In), heptacyclic metallasiloxane cage compound by Volker Lorenz; Cristian G. Hrib; Peter G. Jones; Frank T. Edelmann (37-40).
The unusual heterotrimetallic (Li/Er/In), heptacyclic metallasiloxane cage compound [{(Ph2SiO)2O}3{Li(THF)2}{InMe}]Er (2) has been prepared in 98% yield by reaction of the erbium bis(disiloxanediolate) derivative [{(Ph2SiO)2O}2{Li(THF)2}2]ErCl (1) with trimethylindium, InMe3. The product was structurally characterized by single-crystal X-ray diffraction.The unusual heterotrimetallic (Li/Er/In), heptacyclic metallasiloxane cage compound [{(Ph2SiO)2O}3{Li(THF)2}{InMe}]Er has been prepared in 98% yield by reaction of the erbium bis(disiloxanediolate) derivative [{(Ph2SiO)2O}2{Li(THF)2}2]ErCl with trimethylindium, InMe3. The product was structurally characterized by single-crystal X-ray diffraction.Display Omitted
Keywords: Rare-earths; Erbium; Disiloxanediolates; Indium; X-ray structure;

Assembling coordination ladders with 4′-(4-methoxyphenyl)-4,2′:6′,4″-terpyridine as rails and rungs by Y. Maximilian Klein; Edwin C. Constable; Catherine E. Housecroft; Alessandro Prescimone (41-43).
The divergent ligand 4′-(4-methoxyphenyl)-4,2′:6′,4″-terpyridine (1) reacts with Cd(NO3)2 ·4H2O under room temperature crystallization conditions (MeOH/CHCl3) to give the coordination polymer [{Cd2(1)3(NO3)4} CHCl3 MeOH] n . The polymer adopts a ladder structure with 1 bridging pairs of cadmium(II) centres along both the edges (rails) and rungs of the ladder.4′-(4-Methoxyphenyl)-4,2′:6′,4″-terpyridine (1) reacts with Cd(NO3)2·4H2O under room temperature crystallization conditions to produce a ladder coordination polymer with a Cd to 1 ratio of 2:3; ligand 1 bridges pairs of cadmium(II) centres along both the rails and rungs of the ladder.Display Omitted
Keywords: X-ray; Coordination polymer; Cadmium; Ladder structure;

Mesomeric tautomerism of ligand is a novel pathway for synthesis of cationic dinitrosyl iron complexes: Х-ray structure and properties of nitrosyl complex with thiourea by Nataliya A. Sanina; Sergey M. Aldoshin; Natal'ya Yu. Shmatko; Denis V. Korchagin; Gennadii V. Shilov; Nikolay S. Ovanesyan; Alexander V. Kulikov (44-47).
A new cationic dinitrosyl iron complex (DNIC) with thiourea of the formula [Fe(SС(NH2)2)2(NO)2]Cl·H2O (I) has been obtained in the reaction of aqueous solutions of salts Na2[Fe2(S2O3)2(NO)4]·4H2O and Na2S2O3·5H2O in the presence of SC(NH2)2 in acidic medium for the first time. Structure and properties of I have been studied by X-ray analysis, Mössbauer, IR- and EPR spectroscopy and amperometry. Complex I generates NO in aqueous anaerobic solutions (at T = 25 °C) without additional activation; NO amount at pH 7 and 8 is ~ 36 nM, at pH 9 a smaller (~ 24 nM) but more prolonged release of NO was observed, thus suggesting the potential of this method for synthesis of a new class of DNIC for medicine.The cationic sulfur-containing dinitrosyl iron complex (DNIC) is a new type of NO donors for medicine. Mesomeric tautomerism of thiourea is the key for synthesis of cationic DNICs.Display Omitted
Keywords: NO donors; Sulfur nitrosyl iron complexes; Thiourea; X-ray analysis; IR-spectroscopy; Mössbauer spectroscopy;

[V12O30F4(H2O)2]4 −: One-pot synthesis and characterization of a novel fluorinated dodecavanadate by Lukáš Krivosudský; Peter Schwendt; Róbert Gyepes; Juraj Filo (48-51).
A new synthetic strategy for one-pot synthesis of a fluorinated isopolyvanadate, (NMe4)4[V12O30F4(H2O)2]·9H2O, utilizing peroxidovanadate intermediates, and the stepwise characterization of the reaction mixture is reported herein. The characterization of the title compound was done by single-crystal X-ray diffraction and IR spectroscopy and the reactivity was monitored by 51V NMR spectroscopy to elucidate the hydrolysis pathway. The [V12O30F4(H2O)2]4 − anion consists of four VO5 units in the central layer and two groups of three VO5F units capped by one VO4F(H2O) unit in the outer layers of the anion. In the crystal structure, the anions form strong O–H⋯F hydrogen bonds running in the a axis direction.The synthesis of a novel fluorinated isopolyvanadate with stepwise characterization of the reaction mixture together with structural characterization of the prepared cluster is reported. The title compound was characterized by single-crystal X-ray diffraction and IR spectroscopy and the reactivity was monitored by 51V NMR spectroscopy to elucidate the hydrolysis.Display Omitted
Keywords: Dodecavanadate; Fluoridovanadates; Fluorine; 51V NMR spectroscopy; X-ray diffraction;

A new 3D cobalt(II) complex with left- and right-handed helical channels by Qiu-Ying Huang; Ting Li; Xiang-Ru Meng (52-55).
A new 3D complex, {[Co(btec)0.5(imb)(H2O)]∙1.5H2O} n (1) (imb = 2-(1H-imidazol-1-methyl)-1H-benzimidazole, H4btec = 1,2,4,5-benzenetetracarboxylic acid) has been synthesized by solvothermal technique. X-Ray diffraction analysis indicates that complex 1 displays a 3D framework with left- and right-handed helical channels and very high porous, which can be simplified as a 4,4,4-connected 3D topology with a Schläfli symbol of (32  · 103  · 11)(32  · 104)(32  · 103  · 11). Moreover, its IR spectra, PXRD patterns, thermogravimetric curves, and luminescent emissions were studied at room temperature.A novel 3D complex, {[Co(btec)0.5(imb)(H2O)]∙1.5H2O} n (1), with left- and right-handed helical channels and very high porosity has been synthesized and characterized by single crystal X-ray diffraction. Additionally, its IR spectra, PXRD patterns, TG analyses and fluorescent properties are also investigated.Display Omitted
Keywords: Co(II)-complex; Helical channels; Thermostability; Fluorescence;

Reported here is a novel acylamide MOF, Zn(L) (tdca)·1.5 DMF(1), obtained by a mixed ligand approach, where N4,N4′-di(pyridin-4-yl)-[1,1′-biphenyl]-4,4′- dicarboxamide(L) and thiophene-2,5-dicarboxylic acid (tdca) are used. The 3D framework can be represented as a rare 4-connected self-catenated hxg-d-4-Fddd net with a 65.8 topological symbol. Notably, the MOF shows high CO2 adsorption selectivity over CH4, CO, and N2 gases.We present here a 3D framework with self-catenated structure, which gives 3-fold interpenetration hxg-d-4-Fddd nets. Moreover, the MOF shows high CO2 adsorption selectivity over CH4, CO, and N2 gases.Display Omitted
Keywords: Acylamide MOF; 4-Connected net; Self-catenated net; hxg-d-4-Fddd net; Three-fold interpenetration; Selectively absorbing CO2;

Quinolone based chemosensor for the naked-eye and spectrophotometric detection of Cu2+ in aqueous media by Samadhan R. Patil; Jitendra P. Nandre; Prashant A. Patil; Shilpa Bothra; Suban K. Sahoo; Antonin Klasek; Julián Rodríguez-López; Promod P. Mahulikar; Umesh D. Patil (59-62).
A new 4-hydroxy-2-quinolone based chemosensor (BPHTQ-1) was designed for the spectrophotometric and naked-eye detection of Cu2+. The chemosensor displayed a high selectivity and sensitivity towards Cu2+ in the presence of other competitive metal cations in pure aqueous media. The Cu2+ recognition furnished a distinguishable color change of BPHTQ-1 from colorless to yellow with a significant hyperchromic shift at 300 nm. The S and O atoms of BPHTQ-1 provided a 1:1 binding scaffold for the recognition of Cu2+ ion with a high binding affinity of 19,338 M− 1 and a detection limit of 1.39 μM, which is quite low compared with World Health Organization (WHO) reports.New 4-hydroxy-2-quinolone based chemosensor (BPHTQ-1) was designed for the spectrophotometric and naked-eye detection of Cu2+. Cu2+ recognition furnished with a significant hyperchromic shift at 300 nm. The BPHTQ-1 provided the recognition of Cu2+ ion with a high binding affinity of 19,338 M 1 and a detection limit of 1.39 µM.Display Omitted
Keywords: Chemosensor; Naked-eye detection; Cu2+ ion; Intramolecular charge transfer; DFT;

In crystal engineering, modification of the crystal structure by cation substitution is one of the most important and efficient methods. This paper reveals the origin of the structure transition of a series of (MMgBO3)n (n = 1, M = Li, Na, K, Rb and n = 4, M = Cs) compounds. A force-equilibrium model was established with the comparison of different structures of these compounds. After substituted by other alkali metal cations with different atomic radii, the changed bond between oxygen and cations leads to structural transition. The electronic and optical properties of NaMgBO3, KMgBO3 and RbMgBO3 were also investigated by using DFT methods to give more comprehension of these compounds.The replacement of K+ or Rb+ cations in cubicle structure with smaller Li+ and Na+ cations or larger Cs+ cation leads to the structural transition from cubic to monoclinic space groups.Display Omitted
Keywords: Force-equilibrium model; Structural transition; Cations; Birefringence; Second-harmonic generation;

A novel selective colorimetric chemosensor for Cu2 + in aqueous solution by Hyun Kim; Yu Jeong Na; Gyeong Jin Park; Jae Jun Lee; Yong Sung Kim; Sun Young Lee; Cheal Kim (68-71).
A novel chemosensor 1 (1  = 2-(N-(2-hydroxybenzyl)-N-((pyridin-2-yl)methyl)amino)-N-(2-hydroxyphenyl)acetamide) was synthesized and characterized. The receptor 1 showed a selective colorimetric sensing ability for copper (II) ion by changing color from colorless to yellow in aqueous solution, facilitating naked eye detection of Cu2 +. This phenomenon could be possibly explained by ligand-to-metal charge-transfer. Moreover, 1 could be utilized to monitor Cu(II) over a wide pH range of 3–11. Job plot and ESI-mass analysis indicate the formation of a 1:1 complex of 1 with Cu2 +.A novel chemosensor 1 (1  = 2-(N-(2-hydroxybenzyl)-N-((pyridin-2-yl)methyl)amino)-N-(2-hydroxyphenyl)acetamide) was synthesized and characterized. The receptor 1 showed a selective colorimetric sensing ability for copper (II) ion by changing color from colorless to yellow in aqueous solution, facilitating naked eye detection of Cu2 +.Display Omitted
Keywords: Cu2 +; Colorimetric sensing; Chemosensor; LMCT; Naked eye;

On the synthesis and properties of the MgII complex of perfluorinated octaphenylporphyrazine by Pavel A. Stuzhin; Svetlana S. Ivanova; Oscar I. Koifman; Oleg A. Petrov; Anna Nazarova (72-75).
Reaction of cis-dicyanoperfluorostylbene (1-cis) with MgII butoxide in n-butanol leads to the MgII complex of octa-(pentafluorophenyl)porphyrazine (2), contaminated with by-products due to partial nucleophilic substitution of the fluorine atoms by butoxy groups. Treatment of the MgII complex with CF3COOH gives the metal-free perfluorinated octaphenylporphyrazine (3). The UV–VIS spectral data obtained for the MgII complex 2 and its behavior in CF3COOH solution differs from that reported for the “same” species obtained by cyclotetramerization in the presence of MgII butoxide of the diiminopyrroline derived from dicyanoperfluorostylbene reported recently by S. Kayaköy and E. Gonca [Inorganic Chemistry Communications 21 (2012) 28–31].Reaction of cis-dicyanoperfluorostylbene with MgII butoxide in n-butanol leads to the MgII complex of octa(pentafluorophenyl)porphyrazine, contaminated with by-products due to partial nucleophilic substitution of the fluorine atoms by butoxy groups. Its spectral properties and behavior in CF3COOH solution differs from that reported for the “same” species reported recently by S. Kayaköy and E. Gonca [Inorganic Chemistry Communications 21 (2012) 28–31].Display Omitted
Keywords: Perfluorinated octaphenylporphyrazine; MgII complex; Free-base; Synthesis;

An unprecedented 2D cadmium(II) coordination polymer {[Cd3(L)21,5-dca)6](H2O)}n (1) of potentially tridentate NNN donor Schiff base ligand (L) [L = 1-(4,6-dimethylpyrimidin-2-yl)-2-(dipyridin-2ylmethylene)hydrazine] with the point symbol {43}2{46  · 66  · 83} has been synthesized and characterized by elemental analyses, IR, 1H NMR, emission spectroscopy and single crystal X-ray crystallography. The dicyanamide ions act as linker in the formation of the said coordination polymer. Complex 1 has distorted octahedral geometry around the Cd(II) centers. Interestingly, two different ligand environments are observed around Cd(II) center. Each Cd(L) fragment is connected by three six connecting nodes of [Cd(NCN)6] units to form the 2D coordination polymer of 3,6 connecting binodal system. In addition, the complex molecule gains extra stability by π⋯π interaction.An unprecedented 2D cadmium(II) coordination polymer of tridentate NNN donor of pyrimidine derived Schiff base ligand (L) with the point symbol {43}2{46  · 66  · 83} has been synthesized. Each Cd(L) fragment is connected by three six connecting nodes of [Cd(NCN)6] units to form the 2D coordination polymer of 3,6 connecting binodal system.Display Omitted
Keywords: Pyrimidine based ligand; Cadmium(II) complex; Crystal structure; Dicyanamide bridged 2D polymer;

A solid copper complex with a dimer unit as the building block is assembled through two different hydrogen bonding interactions and features two types of deformable supramolecular rings. As a result, a notable lattice deformation can be observed upon thermal stimulus, owing to the temperature-dependent supramolecular conformation. In addition, its variable-temperature dielectric property was also investigated.A solid copper(II) dicyanamide complex featuring two types of deformable supramolecular rings is reported here, with a notable lattice deformation upon thermal stimulus, owing to the temperature-dependent supramolecular conformation.Display Omitted
Keywords: Lattice deformation; Supramolecular conformation; Dicyanamide complex; Hydrogen bond;

Reported here are two new Cd(II) coordination polymers, namely [Cd2(L)2]n·n(H2O) (1) and [Cd2(L)(4,4-bipy)0.5]n (2) (H2L = 5-(pyridin-2-ylmethoxy)-isophthalic acid, 4,4,-bipy = 4,4′-bipyridine), which were successfully synthesized via the hydrothermal reactions of Cd(NO3)2 and H2L or Cd(NO3)2, 4,4-bpy and H2L. Compound 1 is a 2D layer structure with (3,6)-connected kgd topology, while compound 2 is a 3D pillar-layered framework with (3,4,4)-connected topology. Additionally, the thermal stabilities and luminescent properties of these two compounds were also investigated.Presented here are two new Cd(II) coordination polymers, namely [Cd2(L)2]n · n(H2O) (1) and [Cd2(L)(4,4-bipy)0.5]n (2) (H2L = 5-(pyridin-2-ylmethoxy)-isophthalic acid, 4,4,-bipy = 4,4′-bipyridine). Compound 1 is a 2D layered structure, and compound 2 is a 3D pillar-layered framework.Display Omitted
Keywords: Cd(II) compounds; 5-(pyridine-2-ylmethoxy)-isophthalic acid; Pillar-layered framework; Luminescence;

In recent decades, a large number of reports related to the synthesis of N, O and S containing heterocycles have appeared owing to a wide variety of their biological activity. The metal catalyzed synthesis of heterocycles is becoming an important and highly rewarding protocol in organic synthesis. This review focuses on the use of palladium as a catalyst for the synthesis of oxygen containing five-membered heterocycles. It describes the formation of different types of heterocyclic rings.Palladium-mediated cyclization reactions have been recognized as some of the simplest and useful tools for regio- as well as stereoselective syntheses of carbo- and heterocyclic compounds.Display Omitted
Keywords: Palladium; Catalysis; Heterocycles; Oxygen;

Four two-dimensional lanthanide(III)-4,4-biphenyldicarboxylate complexes: Syntheses, structures, magnetic and luminescent properties by Ying-Bing Lu; Shuang Jin; Shui-Dong Zhu; Shi-Yong Zhang; Guo-Tian Lou; Yong-Rong Xie (120-123).
Four novel Ln-bpdc coordination polymers [Ln(bpdc)(NO3)(DMA)2] [Ln = La(1), Pr(2), Sm(3), Eu(4)] [Ln = lanthanide, H2bpdc = 4,4-biphenyldicarboxylate acid and DMA = dimethylacetamide] have been solvothermally synthesized and structurally characterized by elemental analyses, IR spectra and single-crystal X-ray diffraction. 14 crystallize in the monoclinic space group P21/c and show a 2-D layer constructed from 1-D Ln–organic chain and tetradentate bpdc2 − ligand. The magnetic behavior of 24 has been investigated. The solid-state photoluminescent measurement illustrates that Eu(4) displays the strong fluorescent emissions, which demonstrate that π-rich aromatic organic bpdc2 − ligands can efficiently transfer energy to the EuIII ions. In addition, thermogravimetric analysis of Pr(2) is also described.Four novel Ln-bpdc (H2bpdc = 4,4-biphenyldicarboxylate acid) complexes have been solvothermally synthesized. Complexes 14 are isomorphous, which display a 2-D framework constructed by 1-D [Ln(COO)2] chains and μ 4η 1:η 1:η 1:η 1 bpdc2− ligand. Variable-temperature magnetic studies reveal that Pr(2), Sm(3) and Eu(4) show antiferromagnetic interactions between lanthanide cations. The solid-state photoluminescent measurement illustrates that Eu(4) displays the strong fluorescent emissions and the long lifetime, which demonstrate that π-rich aromatic organic bpdc2 − ligands can efficiently transfer energy to the EuIII ions.Display Omitted
Keywords: Crystal structure; 4,4-Biphenyldicarboxylate acid; Lanthanide(III); Magnetism; Luminescence;

PMMA-supported near-infrared (NIR) luminescent hybrid materials doped with Zn2Ln2-arrayed Schiff-base complexes by Lin Liu; Zhao Zhang; Weixu Feng; Chao Yu; Xingqiang Lü; Wai-Kwok Wong; Richard A. Jones (124-126).
For a series of 4,4′-bpe-linked Zn2Ln2-arrayed Schiff-base complexes [Zn2(L)2Ln2(4,4′-bpe)(NO3)6] (Ln = La, 1; Ln = Nd, 2; Ln = Yb, 3; Ln = Er, 4 or Ln = Gd, 5), degradative chain transfer of the central C=C double bond from 4,4′-bpe within restrains their effective copolymerization with MMA, while PMMA-supported doped hybrid materials PMMA@[Zn2(L)2Ln2(4,4′-bpe)(NO3)6] are obtained, respectively. Their physical properties show that thermal-stability and film-forming properties are distinctively improved while NIR luminescent properties can be retained.Due to degradative chain transfer of 4,4′-bpe within, the Zn2Ln2-arrayed Schiff-base complexes [Zn2(L)2Ln2(4,4′-bpe)(NO3)6] (Ln = La, 1; Ln = Nd, 2; Ln = Yb, 3; Ln = Er, 4 or Ln = Gd, 5) cannot be copolymerized with MMA in the presence of AIBN, while PMMA-supported doped hybrid materials PMMA@[Zn2(L)2Ln2(4,4′-bpe)(NO3)6] are obtained, from which their thermal-stability and film-forming properties are distinctively improved besides the retained NIR luminescent properties.Display Omitted
Keywords: PMMA-supported hybrid materials; Ln3 +-based NIR luminescence; 4,4′-Bpe-linked Zn2Ln2 Schiff-base complexes; Degradative chain transfer;

The quasi-planar trans-[Cu3 II(phen)2(μ-IDC3 −)2(H2O)2]·2H2O (1) and zigzag chainlike {[Cu2 II(phen)2(μ-HIDC2 −)2]·2H2O}n (2) are synthesized, and their crystal structures and solid-state photoluminescence are determined, which indicate that emission intensity can be enhanced and spectra shape can be narrowed by extended planar and octahedral CuII-coordinated geometry separately.Multi-donor ligand H3IDC gives rise to different coordination geometries: quasi-plane and infinite zigzag chain by adjusting pH value in reaction systems with different alkaline substance. Photo-luminescent emission intensity and peak shape can be enhanced and narrowed by extended planar and octahedral CuII-coordinated geometries separately.Display Omitted
Keywords: CuII-complexes; Phen; 4,5-Imidazoledicarboxylic acid; Crystal; Photoluminescence;

Two new Mg(II)-based coordination polymers, {[Mg3(tci)2(DMAC)4]·2DMF}n (1) and [Mg(bci)(H2O)2]n (2) (H3tci = tris(2-carboxyethyl) isocyanurate, H2bci = bis(2-carboxyethyl) isocyanurate, DMAC = N,N′-dimethylacetamide, DMF = N,N′-dimethylformamide), were synthesized by using two similar flexible ligands with different number of arms, and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis, X-ray powder diffraction and TGA. Complexes 1 and 2 exhibit a structure progression from a rare two-dimensional (2D) kgd sheet to a three-dimensional pillar-layer structure involving the layer of Mg(II)–carboxylate connected by bci2 − ligands. The structure dissimilarity between them was dependent on the different number of arms of the two ligands. In addition, the solid state luminescent property and CO2 adsorption of complex 1 were also investigated.Two Mg(II) coordination polymers with different dimensions have been successfully synthesized by selecting the ligands with different number of arms. Complex 1 is a two-dimensional layer which can be represented as a (3,6)-connected 2-nodal net with a kgd topology, while complex 2 exhibits a three-dimensional pillar-layer structure. In addition, complex 1 exhibits extensive solid photoluminescence emission and a high adsorption heat (Q st) for CO2.Display Omitted
Keywords: Coordination polymers; Flexible ligands; Luminescence; Adsorption;

Crystal structures and biological activities of Mn (II) and Cd (II) complexes from an asymmetrical Schiff base ligand by Jing-An Zhang; Yu Li; Yan-Zhong Fan; Xun-Zhong Zou; Ya-Jie Liu; Li-Jie Zhang; Sheng-Run Zheng (136-139).
The Mn(II) and Cd(II) complexes of an asymmetrical Schiff base ligand 4-(1H-benzimidazol-2-yl)-phenyl]-pyridin-4-methyl amine have been prepared by the method of diethyl ether diffusion. The structures of the complexes were identified by elemental analysis (EA), infrared spectra (IR) and single-crystal X-ray diffraction. It was revealed that complexes 1 and 2 were composed of discrete mononuclear structures, and formed schistose structures via two different kinds of hydrogen bonds. The antibacterial and antifungal activities of the ligand and two complexes were tested, which may provide useful information for the research and application in pharmaceutical chemicals.Display Omitted
Keywords: Crystal structures; Antibacterial and antifungal activities; [4-(1H-benzimidazol-2-yl)-phenyl]-pyridin-4-methyl amine; Schiff base;

By incorporating the amide groups into building blocks, two M4L4 molecular tetrahedrons were designed and synthesized for selective recognition of natural saccharides. Tetrahedron Ce–TBSB showed fluorescent enhancement in the presence of natural monosaccharides, whereas the larger analogy Ce–TBAB having twelve additional free amide groups exhibited fantastically selective luminescent enhancement toward sucrose over other natural mono- and di-saccharides. The selective responses of the tetrahedrons thus should be attributed to both the size-fitting of the cavities and the potential hydrogen bond interaction of the amide groups.Two M4L4 cage-like molecular capsules Ce−TBSB and Ce−TBAB were designed, synthesized and characterized for selectively luminescence sensing natural carbohydrates. Ce−TBSB tetrahedron showed selective fluorescent enhancement toward monosaccharides, whereas the larger analogy Ce−TBAB having twelve additional free amides exhibited fantastic selectively toward sucrose over other natural mono−and disaccharides.Display Omitted
Keywords: Metal–organic tetrahedron; Amide groups; Selective recognition; Saccharide;

A first transition–metal coordination polymer [CuH2L(H2O)] n (1) based on a new mixed N-/O-donors 5-[2-carboxy-3-(1H-tetrazol-5-yl)-phenoxy]-isophthalic acid (H4L), which exhibits a 2D 3-connected polymeric network, has been presented and characterized by single-crystal X-ray diffraction, elemental analysis, IR and TGA. It has prominently displayed highly photocatalytic degradation activity for dye degradation as well as antiferromagnetic interactions between the adjacent CuII ions.A first 2D 3-connected copper(II) coordination polymer [CuH2L(H2O)] n (1) based on a new mixed N-/O-donors has been presented. It exhibits highly photocatalytic degradation activity for dye degradation as well as antiferromagnetic interactions between the adjacent CuII ions.Display Omitted
Keywords: CuII compound; Crystal structure; Photocatalytic activity; Magnetic property;

Cyano-bridged Fe2Cu double-zigzag chains: From metamagnetism to coexistence of metamagnetism and single-chain magnet behavior by Peng-Fei Zhuang; Tao Liu; Hui Zheng; Ji-Xiang Hu; Xian-Hui Xie; Ling-Xiang Ren; Wen-Qiang Li; Cheng He; Chun-Ying Duan (147-150).
It is a challenge to tune the magnetic properties of 1D complex via balancing the intra- and interchain magnetic interactions. Utilizing tricyanometalate precursors with different steric hindrance to react with CuII in the presence of 4-styrylpyridine or 4-cyanopyridine, respectively, two cyano-bridged {Fe2Cu} double-zigzag chains [FeIII(Tp)(CN)3]2CuII(4-styrylpyridine)2·3CH3CN·3H2O (Tp = hydrotris(pyrazolyl)borate) (1) and [FeIII(pzTp)(CN)3]2CuII(4-cyanopyridine)2·2CH3CN·H2O (pzTp = tetrakis(pyrazolyl)borate) (2) were obtained. 1 shows metamagnetism with a critical field of 700 Oe, whereas 2 shows the coexistence of metamagnetism and single-chain magnet behavior.Utilizing cyanometalate building blocks with different steric hindrance to tune interchain magnetic interactions, two new cyano-bridged {Fe2Cu} double-zigzag chains were successfully synthesized. The change from metamagnetism to the coexistence of metamagnetism and single-chain magnet behavior was realized.Display Omitted
Keywords: Cyano-bridged complexes; Magnetic relaxation; Magnetic properties; Metamagnetism; Single-chain magnets;

Two porous coordination polymers, {[Cu(2,3-pydc)(bpp)·2.5H2O} n (1) and {[Cu(2,3-pydc)(bpp)·3.5H2O} n (2) (2,3-H2pydc = pyridine-2,3-dicarboxylic acid, bpp = 1,3-bis(4-pyridyl)propane), have been synthesized with the same reactant ratio in different solvents. Two complexes have the same components, coordination environment of Cu(II), as well as the coordination mode of ligands, but represent two quite different porous architectures. 1 is a homochiral 2D → 3D porous polymer with polycatenated layers of achiral ligands. 2 is a 2D centrosymmetric pillared-bilayer porous polymer with water-filled channels. They have been characterized by infrared spectroscopy, elemental analysis, thermogravimetric analysis and X-ray crystallography.The solution reactions of Cu(II), H2pydc and bpp with the same reactant ratio under different solvents resulted in two quite different porous polymers regulated by the conformations of flexible ligands, involving the same components, coordination environment of Cu(II), as well as the coordination mode of ligands.Display Omitted
Keywords: Porous polymer; Homochiral; Pillared-bilayer;

Three coordination polymers based on multidentate N-donor ligands and polycarboxylate anions, namely, [Co3(4,4′-tmbpt)4(btc)2]·9.5H2O (1), [Ag4(4,4′-tmbpt)(btec)(H2O)2]·H2O (2) and [Zn(4,4′-tmbpt)(btec)0.5(H2O)]·0.5H2O (3) (4,4′-tmbpt = 1-((1H-1,2,4-triazol-1-yl)methyl)-3,5-bis(4-pyridyl)-1,2,4-triazole, H3btc = 1,3,5-benzenetricarboxylic acid, and H4btec = 1,2,4,5-benzenetetracarboxylic acid) have been prepared under hydrothermal condition. Compound 1 displays a 3D (3,6,8)-connected framework with (4·62)(44·610·8)(414·612·82) topology. Compound 2 is a 3D (4,5,8)-connected framework with (43·62·8)(43·65·82)(48·62)(410·610·88) topology. Compound 3 exhibits a 2D → 3D polythreading architecture. The photoluminescent spectra indicate that at room temperature, compounds 2 and 3 emit green and blue luminescence, respectively.Two coordination polymers with highly connected structures and one with polythreading architecture have been prepared under hydrothermal conditions, where their photoluminescent properties have also been studied.Display Omitted
Keywords: Coordination polymer; Highly connected; Polythreading; Photoluminescence;

A novel porous molybdophosphate-based FeII,III-MOF showing selective dye degradation as a recyclable photocatalyst by Wei Zhu; Xiu-Yun Yang; Yun-Hui Li; Jian-Ping Li; Dai Wu; Ying Gao; Fei-Yan Yi (159-162).
A novel molybdophosphate-based FeII,III-metal organic framework (FeMoP-MOF) has been synthesized under hydrothermal condition and structurally characterized by elemental analysis, infrared spectroscopy, TGA, and single-crystal X-ray diffraction, namely, {Na6(H2O)12[FeII 2]2[FeIII 4(PO4)][FeII(Mo6O15)2(PO4)8]2}(OH)3·33H2O (1). In 1, every four adjacent sandwich-type FeII[P4Mo6O31]2 clusters are connected into a huge secondary building unit (SBU) with a large trigonal-tapered cage by [PO4] tetrahedra, further being extended into a porous 3D framework by FeII 2 dimers with cross-shaped channels. The central 4-fold [PO4] tetrahedron spirally bridging four FeIII centers resides in the cage and was connected into the SBU. The most interesting feature is that the porous framework exhibits excellent selective degradation for Rhodamine B (RhB) dye as a photocatalyst under visible light irradiation.A novel molybdophosphate-based FeII,III-metal organic framework (FeMoP-MOF) as a recyclable photocatalyst exhibits excellent selective degradation for Rhodamine B dye under visible light irradiation.Display Omitted
Keywords: Molybdophosphate; Porous MOF; Structure; Photocatalyst; Dye degradation;