Inorganic Chemistry Communications (v.65, #C)

Contents List (iii-vii).

The structural determination of two interesting lead(II) coordination polymers, namely [Pb(ind)2(H2O)]n (1) and [Pb2(dbsf)2(bipy)]n (2) (Hind = indane-2-carboxylic acid, H2dbsf = 4,4′-sulfonyldibenzoic acid, and bipy 4,4′-bipyridine), reveals in the second an unexpected polyrotaxane 1D → 1D interpenetrated coordination polymer thanks to the hemidirected coordination geometry of the metal and the rings formed by the dicarboxybiphenyl sulfone ligands along the 1D chain.A novel 1D lead(II) coordination chain gives rise to a polyrotaxane 1D → 1D interpenetrated coordination polymer thanks to the hemidirected coordination geometry of the metal and the rings formed by dicarboxybiphenyl sulfone ligands along the 1D chain.Display Omitted
Keywords: Coordination polymer; Interpenetrated structure; Lead(II) complex; Crystal structure;

Chiral Mn(III) salen complexes grafted on ZnPS-PVPA (zinc poly(styrene-phenylvinyl-phosphonate)-phosphate) upon alkyldiamines through a facile method are evaluated by the asymmetric epoxidation of unfunctionalized olefins. Superior catalytic performances are obtained (conv%, up to > 99; ee%, up to > 99) whenever with m-CPBA or NaClO or NaIO4 as the oxidant. The additives such as NMO, PPNO as well as imidazole play different roles in the corresponding oxidation system. In addition, the supported catalysts could be reused nine times with the retention of their efficiency. These results highlight the potentiality of ZnPS-PVPA as the support for immobilizing chiral salen Mn(III) to be employed in oxidation reactions.The catalysts that alkyldiamines modified ZnPS-PVPA are used for the immobilization of chiral salen Mn(III) display superior catalytic ability either for the experimental scale reactions or for the large-scale reactions.Display Omitted
Keywords: Asymmetric epoxidation; Unfunctionalized olefins; Jacobsen's catalyst; Heterogeneous catalyst; Alkyldiamines;

A luminescent metal–organic framework for selective sensing of Fe3 + with excellent recyclability by Lin Wang; Zhao-Quan Yao; Guo-Jian Ren; Song-De Han; Tong-Liang Hu; Xian-He Bu (9-12).
A new 3D luminescence metal–organic framework with open channels was constructed by the assembling of the zwitterionic H3 LCl ligand and Zn(II) ions under solvothermal conditions. The compound exhibits relatively high luminescence selective sensing for Fe3 + ions with surprisingly excellent recyclability, making it a promising candidate for sensing metal ions in practical.A new 3D luminescence metal–organic framework with open channels was constructed by the assembling of the zwitterionic H3 LCl ligand and Zn(II) ions under solvothermal conditions. The compound exhibits relatively high luminescence selective sensing for Fe3 + ions with excellent recyclability, making it a promising candidate as a fluorescent probe for Fe3 + ions in the field of detection application.Display Omitted
Keywords: Metal–organic framework; Luminescence; Detection; Fe3 +;  Recyclability;

KSbI6O18: An antimony iodate semiconductor material with cyclic chiral S6-symmetric hexaiodate by Guo-Xiang He; Yi-gang Chen; Nan Yang; Mei-Ling Xing; Xian-Ming Zhang (13-15).
The antimony iodate KSbI6O18 which contains cyclic S6-symmetric chiral hexaiodate has been successfully synthesized through hydrothermal reaction. It crystallizes in trigonal space group R-3 with cell parameters of a = 11.3057(6) Å, c = 11.3340(8) Å, γ = 120° and z = 3. Six corner-shared IO4 groups form cyclic S6-symmetric chiral I6O18 groups that are linked by Sb5 + to form anionic [Sb(I6O18)] framework with cavities filled by K+ ions. Optical diffuse reflectance spectra indicate that KSbI6O18 is a potential semiconductor with optical band gap of 2.96 eV.The semiconducting antimony iodate KSbI6O18 has been hydrothermally synthesized, which contains cyclic S6-symmetric chiral hexaiodate linked by Sb5 + to form an anionic [Sb(I6O18)] framework with cavities filled by K+ ions.Display Omitted
Keywords: Antimony; Iodate; Chiral; Semiconductor;

Three novel complexes with helical two dimensional (2D) frameworks, [Ni(Asn)2(H2O)] (1) (HAsn =  l -asparagine), [Cd(Gln)2]n (2) (HGln =  l -glutamine) and [Zn(Gln)2]n (3), have been studied based on X-ray single crystal diffraction analysis. l -asparagine induces two kinds of chirality, the chiral Ni(II) center and the supramolecular M-helixes, into complex 1. l -glutamine induces one kind of chirality, the helixes, into complexes 2 and 3, respectively. Combining the crystal structures of complexes 1–3, the final aggregate chirality induced by coordinated bond interactions can be detected by the liquid state circular dichroism (CD) spectra while the solid state CD spectra of complexes 1–3 additionally reflect the final aggregate chirality induced by weak interactions.The chirality transfer in three novel amino acid complexes was discussed in crystallography. The solution and solid state circular dichroism (CD) spectra of both ligands and complexes were measured to research the sign-to-configuration relationship.Display Omitted
Keywords: Chirality transfer; Helical chains; Liquid state and solid state circular dichroism spectra; Amino acids; Helical two dimensional frameworks; Complex;

Synthesis and crystallographic characterisation of Mg(H2dhtp)(H2O)5·H2O by Susan E. Henkelis; Laura J. McCormick; David B. Cordes; Alexandra M.Z. Slawin; Russell E. Morris (21-23).
A mononuclear complex of composition Mg(H2dhtp)(H2O)5·H2O has been prepared and characterised crystallographically.A new mononuclear Mg-dhtp compound with ligand 2,5-dihydroxyterephathilic acid (dhtp) was prepared and its crystal structure was determined.Display Omitted
Keywords: MOF; CPO-27; Mononuclear; Hydrogen bonding; Reflux;

Structural and photophysical characterization of gold(I) complexes bearing naphthyl chromophores by Elnaz Hobbollahi; Manuela List; Günther Redhammer; Manfred Zabel; Uwe Monkowius (24-27).
We prepared two chlorido-gold(I) complexes of the type L–Au–Cl bearing a naphthyl moiety: Complex 1 with L = tris-1-naphthyl-phosphine shows standard linear coordination without further aggregation in the solid state. Complex 2 with L = 2-naphthyl-isonitrile is engaged in a complex network of aurophilic and π–π interactions. The two complexes show similar luminescence behaviour in solution at room temperature with both intraligand fluorescence and phosphorescence. At 77 K the emission spectra are dominated by intraligand phosphorescence, which is typical of gold complexes with extended π-chromophores.We prepared two chlorido-gold(I) complexes of the type L–Au–Cl bearing a naphthyl moiety (L = tris-1-naphthyl-phosphine and 2-naphthyl-isonitrile). The crystal structures of both complexes were determined and the luminescence properties were investigated.Display Omitted
Keywords: Au(I) complexes; Luminescence; Phosphines; Isonitriles; Naphthyl chromophore;

A new copper(II) selective fluorescence probe based on naphthalimide: Synthesis, mechanism and application in living cells by Guangjie He; Qingtao Meng; Xiuwen Zhao; Cheng He; Peng Zhou; Chunying Duan (28-31).
A new fluorescence probe L based on naphthalimide has been synthesized for selective and quantitative detection of Cu2 + in CH3CN:H2O (4:1, v/v) solution. L exhibited a strong green fluorescence. Upon addition of 2 equiv. of Cu2 +, the fluorescence emission shows a steady and smooth decrease until a plateau is reached with a 30-fold quenching of fluorescence intensity. In the presence of Cu2 +, the absorbance peak of L maximum at 466 nm decreased, and a new absorption band at 600 nm appeared. Under the identical conditions, other physiological and environmental important metal ions induced negligible spectroscopic changes. The 1:2 stoichiometry binding mode of L with Cu2 + was supported by the Benesi–Hildebrand analysis and ESI-MS spectra studies. The detection limit for Cu2 + was estimated to be 64  ppb. Fluorescence microscopy experiments showed that L has practical application in living cells.A new fluorescence probe based on naphthalimide has been synthesized a fluorescent sensor for the selective and quantitative detection of Cu2 + in aqueous solution, and could be application in living cells.Display Omitted
Keywords: Fluorescence probe; Copper; Naphthalimide; Cell imaging;

Treatment of anhydrous ZrCl4 with 3 equiv of lithium 2-(trimethylsilyl) amino-pyridine (TMS-Apy) afforded [(TMS-Apy)3ZrCl] (1) in high yield. The structure of 1 was characterized by spectroscopic and X-ray crystallographic method. The X-ray analysis revealed that 1 was a mononuclear zirconium complex with seven-coordinate metal center and the η 2-coordinated aminopyridinato ligands arranged in a propeller-like fashion. Complex 1 activated with methylaluminoxane (MAO) showed good activity towards ethylene polymerization.A novel N-functionalized organoamide zirconium complex [(TMS-Apy)3ZrCl] (1) has been prepared and characterized. Complex 1 was found to be active for ethylene polymerization.Display Omitted
Keywords: Zirconium; Aminopyridine; Structure; Polymerization of ethylene;

Enantiopure N,N-diamine has been obtained in an economical manner via demetalation of its corresponding dichloro Zn(II) complex, which is separated by fractional crystallization of two diastereomeric Zn(II) complexes. Polymerization of rac-lactide (rac-LA) initiated by diisopropoxide derivative proceeds rapidly at room temperature in a living fashion to yield heterotactic polylactide (PLA) with Pr  = 0.90.Herein, we have reported the facile and economical way to obtain enantiopure N,N-diamine via demetalation of its corresponding dichloro Zn(II) complex, which is obtained by fractional crystallization of two diastereomeric Zn(II) complexes. Diisopropoxide Zn(II) complex generated is situ polymerize racemic lactide within 3 min to yield heterotactic PLA with Pr  = 0.90.Display Omitted
Keywords: Enantiopure zinc complexes; X-ray structure; Ring-opening polymerization; Double active site catalysts; Heterotactic-enriched polylactide;

The complexes M(II)(binap)Cl2 with M = Ni and Pd and binap = 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl show an IL phosphorescence in the solid state under ambient conditions. The nickel(II) complex is a unique example of a triplet emitter. Generally, any triplet emission of Ni(II) complexes is quenched by non-emissive low-energy LF excited states. In the case of the binap complex, the LF states are apparently located at energies well above the IL triplet.Solid Ni(II)(binap)Cl2 shows a binap IL phosphorescence under ambient conditions although nickel is not known to exert the classical heavy-atom effect.Display Omitted
Keywords: Nickel; Palladium; Binap; Luminescence; Triplet emitter;

Luminescence properties of a thermal-responsive organogel to various metal cations by Jusheng Xie; Changjuan Chen; Xinxian Ma; Jincai Wu (41-44).
A new gelator (L) containing Schiff base, benzoimidazol and naphthayl moieties was synthesized and its self-assembly was investigated in various solvents. Gelation test revealed that it could form a thermal-responsive gel in ethylene glycol (GL) or the mixture solution of ethylene glycol and DMF. Different fluorescence behaviors were observed upon adding different metal ions. The addition of Mg2 + maintained the gelating ability of L, meanwhile the Mg2 +-ion-mediated organogel in ethylene glycol can enhance the fluorescence of GL. The addition of Al3 + can destroy GL and lead to a state transition from gel to clear solution; the solution can give a brilliant blue emission excited at 365 nm UV. Interestingly, the luminescence of GL increased sharply at first but decreased finally. The fluorescence of GL was quenched when other metal cations were added.A thermal-responsive organogel can be obtained in ethylene glycol and its self-assembly was investigated in various solvents. The organogel shows unique behavior upon adding Al3 + in comparison to other metal cations. The results show the addition of Al3 + can destroy the gel and lead to a state transition from gel to clear solution; the solution can give a brilliant blue emission excited at handheld 365 nm UV lamp, interestingly the luminescence of gel increases sharply at first but followed by a decrease finally.Display Omitted
Keywords: Gelator; Fluorescence behaviors; State transition; Mg2 +-ion-mediated organogel;

A novel cobalt(II) metal–organic framework based on an unprecedented ribbon-shaped secondary building unit by Wei Meng; Shuang Xu; Zhengrui Zhang; Shuqi Yu; Jikang Yu; Lei Dai; Ling Wang; Hongwei Hou (45-48).
A novel 3D metal–organic framework (MOF) {[Co2.5(dcpp) (μ 3-OH) (μ-H2O)]·H2O} n (H4dcpp = 4,5-bis(4′-carboxylphenyl)-phthalic acid) with unprecedented ribbon-shaped secondary building units (SBUs), has been synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, and IR. In addition, the thermal stability and magnetic behavior of the complex were also investigated.This work reports a novel cobalt(II) metal–organic framework based on an unprecedented ribbon-shaped secondary building unit. The complex represents the first example of MOF built from high nuclear ribbon-shaped SBU. Furthermore, the study of magnetic property indicated that dominant antiferromagnetic coupling interactions existed between the adjacent Co(II) centers.Display Omitted
Keywords: Metal–organic framework; SBUs; Ribbon-shaped; Cobalt(II); Magnetic behavior;

Double-linked chain in POM-based hybrids. Synthesis, crystal structure and properties of an inorganic–organic compound by Yan Guo; Xiao-Min Li; Tian Shi; Chunhe Li; Ya-Guang Chen; Hong-Ye Wang (49-53).
An inorganic–organic compound, (H2bipy)3[(H2O)2Cu2(bpy)3(PMo11CuO39)2]·8H2O(1) (bpy = 4,4-bipyridine), has been prepared under mild hydrothermal conditions and has been structurally characterized by single-crystal X-ray diffraction. In compound 1 the polyoxoanion PMo11CuO39 5 − has a pseudo-Keggin structure since the Cu(II) atom replaces one Mo(VI) atom of Keggin anion. The polyoxoanions share their terminal oxygen atoms creating an anionic chain. Two adjacent anions in the chain coordinate to same one Cu ion forming a double-linked anionic chain, and then a railway-like chain is constructed by linkage of the bipy molecules to Cu atoms in which the double-linked anionic chains act as two rails of the railway and bipy molecules act as “crosstie”. The 3D supramolecular structure is formed from the railway-like chains through hydrogen bonds and strong π…π stacking interactions. The fluorescent emission of compound 1 from 4,4′-bipyridine ligand was detected and the photocatalysis property for degradation of methylene blue (MB) of compound 1 upon a UV irradiation was examined.A 1-D railway-like framework build by mono-copperII substituted molybdophosphate units and [Cu2(bipy)3] complex has been synthesized and characterized structurally. The electrochemical properties of the title compounds are also investigated.Display Omitted
Keywords: Polyoxometalates; Polyanion chain; Hydrothermal synthesis; Photocatalytic property;

A novel 3D heterometal–organic coordination polymer [{K2(H2O)6} {Cu3(Hpimdc)2(CN)2}{Cu2(H3pimdc)2(CN)}]·2H2O (1) (H3pimdc = 2-propyl-1H-imidazole-4,5-dicarboxylic acid) has been synthesized under hydrothermal conditions and characterized by elemental analysis, IR, PXRD, UV–vis, and single-crystal X-ray diffraction. In complex 1, adjacent K+ ions are linked through H3pimdc to form binuclear chain units {K2(H2O)6}n, which connect with unique Cu-cyanide complex linker {Cu3(CN)2(Hpimdc)2} to form 2D layers. The 2D layers are further connected via another linkage unit {Cu2(CN)(H3pimdc)2} to form 3D frameworks with (41162)2(334251101123164) topology. The H3pimdc ligand in 1 exhibits μ 2- and μ 4-two kinds of coordination fashions. In addition, the N2 adsorption, fluorescence, and photocatalytic properties of polymer 1 are evaluated detailed.A novel 3D heterometal–organic coordination polymer is synthesized. In the polymer, adjacent K+ ions are linked through H3pimdc to form a binuclear chain unit, which connects with the unique building block {Cu3(CN)2(Hpimdc)2} to form a 2D layer. The layers are further linked via {Cu2(CN)(H3pimdc)2} to form a 3D network with 1D channel. Polymer 1 exhibits fluorescent properties and good degradation ability for MB under UV light.Display Omitted
Keywords: Heterometal–organic materials; {CuCN}; Binuclear K oxo-cluster units; Fluorescent property; Photocatalytic activity;

Two cobalt complexes derived from 1H-1,2,3-triazole-4,5-dicarboxylic acid: Syntheses, structures and magnetic properties by Ling Li; Ji-Yong Zou; Zhen Gu; Sheng-Yong You; Yan-Hua Chen; Jun Xia; Jian-Zhong Cui (59-62).
Two cobalt(II) homometallic complexes, [Co2(HTDA)2(H2O)6·2H2O] (1) and {[Co3(TDA)2(H2O)8]·H2O} n (2) (H3TDA = 1H-1,2,3-triazole-4,5-dicarboxylic acid) have been synthesized and structurally characterized in detail. Single-crystal X-ray crystallographic study reveals that they crystallize in trigonal space group R-3 and orthorhombic space group Pna21, respectively. In 1, two Co2 + cations are bonded by two HTDA2 − ligands to generate a binuclear CoII unit, which can further be extended to a 3D supermolecular structure via the hydrogen bonds. At variance with 1, the nearest Co2 + cations of 2 are connected via TDA3 − ligands to form a 1D coordination polymer and can be further linked to each other to result in a 3D supermolecular framework through the hydrogen bonding interactions as well. The magnetic properties of them were studied in detail.Two cobalt(II) homometallic complexes derived from 1H-1,2,3-triazole-4,5-dicarboxylic acid were synthesized and fully characterized. The magnetic properties were studied in detail to determine the following magnetic parameters: g  = 2.47, D  = 36.85 cm− 1, zJ  = − 0.61 cm− 1, and R  = 0.9979 for 1; A  +  B  = 9.79 cm3  K mol− 1, E 1  = − 31.27 K, E 2  = − 1.55 K and R  = 0.9998 for 2, respectively, suggesting dominant antiferromagnetic interaction between Co2 + ions.Display Omitted
Keywords: Cobalt(II) complexes; H3TDA ligand; Hydrogen bonding interactions; Magnetic properties;

Bis-boron-capped tris(dioxime) cage complexes with terminal carbonyl groups by Jialong Zhang; Zhiyan Ma; Haiyang Zhao; Chunhua Ge; Yuhui Wang; Xiangdong Zhang (63-67).
Three clathrochelate complexes, [(p-OHCC6H4B)2(chdd)3FeII]·0.5CH2Cl2 (1·0.5CH2Cl2, H2chdd = 1,2-cyclohexanedione-1,2-dioxime), [(p-OHCC6H4B)2(hmbd)3MnII 2]}·Et3NH·0.5CH3OH·0.5H2O (2·0.5CH3OH·0.5H2O, H3hmbd = 2-hydroxy-5-methyl-1,3-benzenedicarboxaldehyde-1,3-dioxime), and [(p-OHCC6H4B)2(hmbd)3CoII 2]·Et3NH·H2O (3·H2O), were synthesized through template macrobicyclization using metal-oximates as building blocks. These complexes contained reactive apical formyl substituents. FeII in mononuclear complex 1 was wrapped in the cavity formed by condensation of H2chdd with 4-formylphenylboron acid. The organic frameworks of anion unit of binuclear MnII complex 2 and that of binuclear CoII complex 3 were combined by H3hmbd with 4-formylphenylboronic acid. Spectroscopic, electrochemical characterizations of complexes 13 were exploited. DFT calculation of 1 and 2 was also done for better understanding of the electronic property and charge carrier mobility.Complexes of electroneutral mononuclear and anionic binuclear cage complexes with metal oximates cores are described. Terminals of the cage are capped by tetrahedral boron atoms through covalent and coordinate B–O bonds. Theoretical investigation for the electron distribution of the complexes under external electric field of different strengths and directions indicates that the complexes are sensitive to the electric field.Display Omitted
Keywords: Clathrochelates; Ligand reactivity; Charge transport; Calculation;