Inorganic Chemistry Communications (v.75, #C)

Contents List (iii-vi).

Zwitterionic phthalocyanine zinc (II) synthesis, and photodynamic activity comparison with nonionic and cationic phthalocyanine by Li Gui; Quanquan Zhang; Yue Wang; Kelong Fang; Ao Wang; Xin You; Lin Zhou; Jiahong Zhou; Shaohua Wei (1-4).
Zwitterionic structures were helpful for solubility, cellular uptake and activity for many drugs. But few researches about the influence of zwitterionic structures on phthalocyanine were reported. So, in this work, we design and synthesis a zwitterionic zinc (II) phthalocyanines(ZnPcs). And its solubility, photochemical and photodynamic activity to cancer cells was investigated. Furthermore, these properties of other two ZnPcs, nonionic and cationic ZnPcs with same major structure, were also researched simultaneously. Comparative studies indicated that the zwitterions structures could improve the solubility of ZnPc but greatly reduced its reactive oxygen species (ROSs) generation ability and anti-cancer activity in vitro to nonionic and cationic ZnPcs.A novel zwitterionic sulfobetaine ZS-ZnPc has been synthesized, and the photophysical, photochemical and photobiology properties were compared with other two ZnPcs (NI-ZnPc and CA-ZnPc).Display Omitted
Keywords: Zwitterionic; Sulfobetaines; Phthalocyanine; Photodynamic therapy;

A new ring-shaped Cr-containing tungstophosphate based on [H2P2W12O48]12− by Jipeng Guo; Yaqing Zhao; Chao Zhang; Pengtao Ma; Dongdi Zhang; Jingyang Niu; Jingping Wang (5-7).
A new Cr-containing tungstophosphate [(Cr(H2O)2)3(H2P2W12O48)3]27 − (1a) was prepared via simple, one-pot reaction method, which was isolated as hydrated potassium salt, K4[H23(Cr(H2O)2)3(H2P2W12O48)3]·34H2O (1). Compound 1 was characterized by single-crystal X-ray diffraction, FT-IR, UV-vis, elemental analyses, thermal analysis, electrochemistry and electrospray ionization mass spectrometry. Polyoxoanion 1a is composed of three {P2W12} subunits linked by three {Cr(H2O)2} bridges alternately, forming a ring in a corner-sharing mode. Moreover, variable temperature magnetic susceptibility indicates that 1 shows antiferromagnetic behavior.A new Cr-containing trimeric tungstophosphate [(Cr(H2O)2)3(H2P2W12O48)3]27 − based on [H2P2W12O48]12 − building block has been prepared and characterized.Display Omitted
Keywords: Electrochemistry; ESI-MS spectrum; Magnetic studies; Tungstophosphate;

Two bipyridinium-based coordination polymers, {[Cd(BCbpy)2(o-BDC)]·13H2O} (1) and {[Cd(BCbpy)2(SA)]·6H2O} (2), have been synthesized and structurally characterized. Single-crystal X-ray diffraction analysis shows that the two compounds have similar one-dimensional coordination polymeric chain structures but different packing patterns. Compound 1 displays fast eye-detectable photochromic behavior while compound 2 is photoinert under 365 nm irradiation. The influence of different substituent groups in same site of auxiliary ligands on the photochromic behaviors of the two compounds has been studied in detail.The effect of different substituent groups in the same position of auxiliary ligands on the photochromic behaviors of bipyridinium-based coordination polymers has been explored.Display Omitted
Keywords: Coordination polymers; Bipyridinium; Photochromism;

A novel inorganic-organic hybrid polyoxotungstate H4[Ni(en)2]2[Ni(en)(dap)]2[Ni(dap)2]2[Ni4(en2)(PW9O34)2]-{[Ni(H2O)5]2[Ni4(en)2(PW9O34)2]}·12H2O (1, en = ethylenediamine, dap = 1,2-diaminopropane) has been successfully synthesized under hydrothermal conditions and structurally characterized by single-crystal X-ray diffraction, powder X-ray diffraction, infrared spectroscopy, elemental analysis and thermogravimetric analysis, respectively. Single-crystal structure analysis reveals that 1 exhibits a 2-D network structure based on two kinds of tetra-Ni-substituted sandwich-type Keggin polyoxoanions linked by different types of Ni-organoamine complexes.Graphic abstractDisplay Omitted
Keywords: Polyoxometalate; Hydrothermal synthesis; Sandwich-type structure; Nickel complex;

A novel Keggin-type molybdophosphate-based helix metal-organic chain and its polypyrrole composite: Synthesis, structure and properties by Xiuli Wang; Huixiu Zhang; Xiang Wang; Tianjiao Li; Na Li; Na Xu; Hongyan Lin; Guocheng Liu (16-20).
A novel Keggin-type molybdophosphate-based hybrid containing left- and right-handed helical chains, {Ag[H2(3-bptzh)](PMo12O40)}·H2O (1) [3-bptzh = 1,6-bis(5-(3-pyridyl)-tetrazolyl)hexane], has been synthesized under hydrothermal condition, and characterized by IR spectra, elemental analyses, single crystal X-ray diffraction and powder X-ray diffraction. The helix metal-organic chain [AgH2(3-bptzh)]n 3 + is constructed from the flexible 3-bptzh ligands and Ag atoms, on which [PMo12O40]3 − polyoxoanions are hanged via Ag―O bonds. The structural feature is fascinating and scarcely reported in POM-based complexes. The electrochemical, fluorescent and photocatalytic properties of the title compounds have been investigated. Additionally, the polypyrrole (PPy) composite material of 1 (PPy/1) has been prepared by loading polypyrrole on the surface of compound 1, which shows excellent photocatalytic activities for degradation of organic dyes under visible light irradiation.A novel Keggin-type molybdophosphate-based hybrid containing left- and right-handed helical chains, {Ag[H2(3-bptzh)](PMo12O40)}·H2O (1), has been synthesized. The polypyrrole composite of 1 demonstrates excellent photocatalytic activity for the decomposition of MB and RhB under visible light irradiation.Display Omitted
Keywords: Polyoxometalate; Helix metal-organic chain; Polypyrrole composite; Photocatalysis;

Biosorption and extraction of europium by Bacillus thuringiensis strain by Xiaohong Pan; Wei Wu; Jian Lü; Zhi Chen; Lan Li; Wenhua Rao; Xiong Guan (21-24).
Biosorption features of europium on Bacillus thuringiensis biomass have been studied to explore the potential of biomass for extracting Eu3 + from aquatic systems. The adsorption isotherm has been fitted with Langmuir model, the adsorption capacity of Eu3 + achieves as high as 160 mg/g and adsorption kinetics follows pseudo-second order rate model. Additionally, the bacteria exhibit relatively low Eu3 + adsorption characteristics at pH < 4, and the salinity concentration shows no obvious impact on Eu3 + biosorption. The SEM-EDS analysis indicates Eu3 + has been adsorbed on bacterial surfaces. Desorption and recycle experiments demonstrate that Eu3 + could be well desorbed by HCl or EDTA solution, and the bacteria exhibit good regeneration and reusability. These results confirm that the bacteria could be excellent biosorbents for Eu3 +.A strategy was designed for the recovery of Eu3 + from water. The adsorption mechanism and efficiency between B. thuringiensis and Eu3 + were evaluated. The bacteria had high adsorption capacity and the adsorbed Eu3 + could be desorbed by HCl or EDTA solution, which implies that bacteria could be an excellent biosorbent for extraction and recovery of low concentrations of Eu3 +.Display Omitted
Keywords: Europium; Bacillus thuringiensis; Biosorption; Desorption; Recycle;

Fluorescence response and detection of Cu2 + with 2-(2-hydroxyphenyl)benzimidazole in aqueous medium by Minghao Qin; Dan Jin; Weilong Che; Yang Jiang; Liping Zhang; Dongxia Zhu; Zhongmin Su (25-28).
We present a simple but highly selective and sensitive fluorescence probe for Cu2 + in aqueous medium: 2-(2-hydroxyphenyl)benzimidazole (L1). The probe can be applied to the monitoring of Cu2 + with wide pH range from 6 to 11 and used in biological imaging for the detection of Cu2 + in living cells.Display Omitted
Keywords: Fluorescence; Copper; Benzimidazole; Biological application;

Through the radical copolymerization of MMA (methyl methacrylate) with a vinyl-containing complex monomer {[Yb4(L)2(HL)2(μ 3-OH)2(NO3)2]·(NO3)2} (1; H2L =  N,N′’-bis-(5-(3′-vinylphenyl)-3-methoxy-salicylidene)cyclohexane-1,2-diamine), the first example of PMMA-supported and Yb4(Salen)4-containing metallopolymer Poly(1-co-MMA) exhibits significantly improved physical properties besides relatively higher NIR quantum yields (Φ Yb Yb  = 1.18% and Φ L Yb  = 0.86%) than those (Φ Yb Yb  = 1.02–1.04% and Φ L Yb  = 0.73–0.75%) of complex monomer 1 in solution and 1@PMMA in solid state.For the first-example of PMMA-supported while Yb4(Salen)4-containing metallopolymer Poly(1-co-MMA), the significantly improved physical properties including relatively higher Yb3 +-centered NIR quantum yields (Φ Yb Yb  = 1.18% and Φ L Yb  = 0.86%) than those (Φ Yb Yb  = 1.02% and Φ L Yb  = 0.73%) of complex monomer 1.Display Omitted
Keywords: Vinyl-containing Ln4(Salen)4-arrayed complex monomer; Metallopolymer; Yb3 +-centered NIR luminescence; Radical copolymerization;

Structurally modified CMPO functionalized pillar[5]arenes in ionic liquid were found to be highly efficient, and radiolytically stable systems for the selective separation of thorium. The extraction was demonstrated to proceed via ‘cation exchange’ mechanism through [Th.L (NO3)]3 + species while the DFT calculation was used for understanding the optimized ligand structure and its complexation with Th4 + ion in ionic liquid. Oxalic acid was found to be successful for almost quantitative back extraction of thorium from CMPO functionalized pillar[5]arene complex in ionic liquid.Display Omitted
Keywords: CMPO; Thorium; Pillar[5]arenes; Extraction; Mechanism;

A Pb(II)-Na(I) coordination polymer, {[Pb3NaL3](Me2NH2)2(C2H5OH)1.5(H2O)10.5} n (1) (H3L = 4,4′,4″-s-triazine-2,4,6-triyl-tribenzoic acid), was synthesized under solvothermal condition. This structure crystallizes in the orthorhombic system and shows a 3D pillar-layer network. Topologically, it shows complicate (3,4,5,6,7)-connected net with Schläfli symbol of (42·68·89·102)(43·62·8)2(43·66·8)2(48·66·8)(63). Luminescent investigations reveal that 1 can detect Fe3 + with relative high sensitivity and selectivity, and show broad linear range of 0–1000 μM, as well as low detection limits of 8.65 nM for Fe3 +.A heterometallic Pb(II)-Na(I) coordination polymer has been synthesized, which showed high sensitivity and selectivity to luminescently detect Fe3 +.Display Omitted
Keywords: Coordination polymer; Fluorescent probe; Fe3 + sensing;

Synthesis, characterization, crystal structure and in vitro anticancer potentials of mono and bimetallic palladium(II)–N–heterocyclic carbene complexes by Mohammed Z. Ghdhayeb; Rosenani A. Haque; Srinivasa Budagumpi; Mohamed B. Khadeer Ahamed; Amin Malik Shah Abdul Majid (41-45).
N–heterocyclic carbene (NHC) complexes of palladium(II) are generally active as catalysts toward various coupling reactions, while their pharmacological efficiencies are seldom explored. A new series of palladium(II) complexes of both, functionalized and non–functionalized NHCs that were active against the human colon cancer (HCT116) cells are reported. Complexes were prepared by the technique of transmetallation using palladium source and in situ prepared silver(I)–NHC complexes in acetonitrile, and all complexes are characterized using spectroscopic and analytical tools. Additionally, the structure of palladium complex 9 was elucidated using single crystal X–ray diffraction method. In vitro anticancer studies revealed that the palladium complexes, 9 and 10, having xylyl–spacers significantly inhibited the HCT116 cell growth, exhibiting IC50 values in low micromolar range in MTT assay.Display Omitted
Keywords: Anticancer activity; HCT116; MTT assay; Palladium–NHC complex; X–ray diffraction;

Solvent-free synthesis of new metal phosphate-oxalates with helical-chain and slablike structures by Wei Wang; Lindong Luan; Meng Yang; Kangcai Wang; Zhien Lin (46-48).
Two metal phosphate-oxalate, namely, H3pmdeta ⋅ Ga2(HPO4)(H2PO4)(C2O4)3 (1) and H2mpip ⋅ Mn2(H2PO4)2(C2O4)2  ⋅ H2O (2), were prepared under solvent-free conditions, where pmdeta = N′,N″,N″-pentamethyldiethylenetriamine and mpip = 1-methylpiperzaine. Compound 1 features a helical-chain structure containing cyclic inorganic building block. Compound 2 has a slablike structure with a kgd net. The magnetic and proton-conducting properties of compound 2 were also investigated.Two new metal phosphate–oxalates were prepared under solvent-free conditions. They have helical-chain and slablike structures templated by different amines. The slablike compound exhibits a humidity-dependent behavior of the proton conductivity.Display Omitted
Keywords: Solvent-free synthesis; Inorganic-organic hybrid solids; Phosphate; Oxalate; Proton conductivity;

The reaction of 2,2-bipyridine (bpy), NiCl2·6H2O and tetracyanoethylene (TCNE) affords a nickel complex, [Ni(bpy)3]⋅(PCPP)2 1 (PCPP: pentacyanopropenide, a compound derived from TCNE). Its structure has been characterized by physics-chemical and spectroscopic methods. This complex can electrocatalyze hydrogen generation both from acetic acid, with a turnover frequency (TOF) of 152.88 mol of H2 per mole of catalyst per hour an overpotential (OP) of 941.6 mV (in CH3CN), and from aqueous buffer (pH 7.0) with a TOF of 1464 mol of H2 per mole of catalyst per hour at an OP of 837.6 mV.Display Omitted
Keywords: Nickel complex; Molecular catalyst; Proton or water reduction; H2 evolution;