Hydrothermal in situ Ligand Synthesis from 1,10-Phenanthroline-5,6-dione and Characterization of 1D Coordination Polymers [Co(bpdc)(H_2O)_3]·H_2O and [Cu(bpy)V_2O_6]

Hydrothermal treatment of MCl2 （ M = Co or Cu ） , NH4 VO3, and 1,10-phenanthroline-5,6-dione （pdon） resulted in the formation of a duplex coordination polymer [ Co （ bpdc ） （ H2O ） 3 ] · H2O （ bpdc = 2,2＇-bipyridine-3,3＇-dicarboxylate） and a chain-like coordination polymer [ Cu （bpy） V2O6 ] （ bpy = 2,2＇-bipyridine ）. X-ray single-crystal structural analysis shows that under hydrothermal conditions and in the presence of different transition metals, the organic reagent pdon was transformed in situ into bpdc and bpy, respectively. Mechanism of the in situ ligand synthesis reaction has been discussed.

A New Tetranuclear Cubane-like Ni(Ⅱ) Complex Based on Schiff-base Ligand:Synthesis,Crystal Structure and Magnetic Properties

A new Ni（Ⅱ） cubane-like complex, namely, [Ni（L）（CH3OH）]4·（CH3OH）2, has been obtained via self-assembly of nickel（Ⅱ） and Schiff base, where the ligand L is a raceme of（R）-2-[（2-hydroxy-1-phenyl-ethylimino）-methyl]-6-methoxy-phenol. X-ray diffraction analysis reveals that the complex shows a cubane-like [Ni4O4] cluster and similar coordination environment around the metallic centers. Magnetic measurements indicate there is ferromagnetic interaction within the Ni4 cluster.

Synthesis of Imidazole Cyclophane as Ligand of Binuclear Metalloprotein Models

Four imidazole cyclophanes have been synthesized by the oxidation of bis-imidazoline with barium manganate followed by cyclization with 2,6-bis(bromomethyl) pyridine in the presence of NaH. All the compounds were identified by IR, (HNMR)-H-1, MS and elemental analysis.

Synthesis and Crystal Structure of a New Zinc(Ⅱ)Coordination Polymer Assembled by 4-Nitrophthalic Acid and Bis(imidazol)Ligands

A new complex [Zn（4-nph）（bib）]（2n）·nH2O（1） has been obtained by the reaction of metal（Zn（Ⅱ））,1,4-bis（imidazol-1-yl）-butane（bib） with 4-nitrophthalic acid（4-H（2nph））.The crystal structure of 1 has been determined by single-crystal X-ray diffraction analysis.Compound 1 is of triclinic system,space group P1 with a = 10.3251,b = 12.4503,c = 16.6497 A,α = 88.487（3）,β = 72.529（3）,γ = 79.991（3）°,V = 2009.8（5）A^3 and Mr = 945.47.Complex 1 shows a three-dimensional（3 D） framework.Moreover,through intermolecular hydrogen bonds,compound 1 is assembled into a supramolecular structure.The thermal stability and luminescent properties of 1 are also investigated.

Synthesis of Novel Polypyridine Ligands

Some novel polypyridine ligands containing adsorbing groups were synthesized with the purpose of developing new ruthenium(II) polypyridine complexes to be used in solar cell based on dye-sensitized nanocrystilline TiO2 film electrode.

The Synthesis of New Sulfur-containing Chiral Macrocyclic Ligands

Five new chiral sulfur-containing macrocyclic ligands which can be used in chiral recognition to guests have been synthesized and characterized

ASYMMETRIC SYNTHESIS WITH ORGANO-TITANATE REAGENTS COORDINATED BY TARTARATE-LIKE LIGAND

A series of substituted chiral benzhydrols were synthesized by the reaction of aromatic aldehydes with chiral intermediates formed from chiral titanates and arylmagnesium halides.

SYNTHESIS AND CHARACTERIZATION OF A NOVEL DITOPIC LIGAND AND ITS HETEROMETALLO-BINUCLEAR COMPLEX

A ditopic ligand bpy-cyclam(L)and its heterometallo-binuclear complex Ru(bpy)_2(bpy-cyclam-Ni)(ClO_4)_43H_2O(3)designed for use in the catalytic photoreduction of carbon dioxide have been newly synthesized and characterized.The protonation constants of L were also determined.

Mononuclear and Dinuclear Yttrium Complexes Supported by Pyrrolide Ligands： Syntheses, Structures and Catalytic Behaviors towards the Ring-opening Polymerization of ε-Caprolactone

The syntheses, structures and catalytic activities of two yttrium complexes supported by pyrrolide ligands are reported. Treatment of Y（N（Si Me3）2）3 with one equivalent of H3bptd（H3bptd = 1,9-bis（2-pyrrolyl）-2,5,8-triazanona-1,8-diene） in THF gave a complex of composition [Y（bptd）（THF）]2（1）. Reaction of Y（N（Si Me3）2）3 with one equivalent of H3tpa（H3tpa = tris（pyrrolyl-α-methyl）amine） in THF generated [Y（tpa）（THF）3]（2） in good yield. Complexes 1and 2 have been characterized by single-crystal X-ray diffraction, elemental analyses and NMR spectroscopy. Complex 1 is dinuclear. The two metal centers are doubly bridged by two amine nitrogen atoms to form a Y–N–Y–N four-membered rhombus ring. The geometries of Y^3＋ ions in 1and 2 are well described as pentagonal bipyramid and capped octahedron, respectively. The ring-opening polymerization reactions of ε-caprolactone initiated by 1 and 2, respectively, were investigated. They both exhibited good catalytic activity for the polymerization of ε-caprolactone. All of the obtained polymers have high molecular weights and relatively narrower PDIs. The polymers generated by 2 possessed polydispersity close to 1.1. The good catalytic activities of 1 and 2 reveal their potential applications in polymer industry.

A Novel Two-dimensional Homochiral Zinc(Ⅱ) Complex Constructed Based on In Situ Ligand Formation

A novel zinc（II） complex, Zn（IBT）2 （1, H1BT = 5-（4-（（1H-imidazol-1-yl）methyl）- phenyl）-2H-tetrazole） has been synthesized with Zn（NO3）2·6H2O, 4-（imidazol-l-ylmethyl）benzonnitrile （IBN） and NaN3 by the hydrothermal method, and characterized by elemental analysis, IR and single-crystal X-ray diffraction. Crystallographic data for 1： C22H18N12Zn, Mr = 515.85, orthorhombic, Pbcn, a = 16.0567（15）, b = 9.5316（9）, c = 14.6107（14） A, V= 2236.1（4） A3, Z= 4, Dc = 1.532 g/cm3,μ = 1.138 mm-1, F（000） = 1056, R = 0.0350 and wR = 0.0888 for 1438 observed reflections （I 〉 2σ（I）） and the goodness-of-fit S = 1.002 on F2. The crystal structural analysis revealed that complex 1 exhibits a rare two-dimensional homochiral wave-like layer structure. In addition, the photoluminescence of complex 1 was studied in the solid state at room temperature together with its theoretical analysis.

Synthesis,Characterization and Molecular Structure of a Diiron Complex(μ-SCH_2CH_2CH_2S-μ)Fe_2(CO)_5(Ph_2PCH_3)

The title complex,（μ-pdt）Fe_2（CO）_5（Ph_2PCH_3）（pdt = SCH_2CH_2CH_2S）,was obtained by the reaction of the parent complex（μ-pdt）Fe_2（CO）_6 with Ph_2PCH_3 and Me_3NO·2H_2O in good yield（90%）. The title complex was characterized by IR,~1H NMR,^（31）P{~1H} NMR and ^（13）C{~1H} NMR spectroscopy as well as by single-crystal X-ray diffraction analysis. The molecular structure shows that the title complex contains a butterfly diiron propanedithiolate cluster with five terminal carbonyls and a monophosphine ligand Ph_2PCH_3. The crystal packing diagram reveals that intermolecular C H···O hydrogen bonds between CH_2 and carbonyls,π-π stacking interactions and van der Waals＇ interactions stabilize the solid state to form a three-dimensional network.

Syntheses and Crystal Structures of Two Copper(Ⅱ) Coordination Polymers Derived from Aromatic Carboxylic Acids and Bis(imidazoles)Ligands

Two compounds have been obtained by the reaction of metal（Cu（II））, 4,4＇-bis（imidazol-l-yl）diphenyl thioether（BIDPT） with two carboxylic acids, 4,4＇-oxydibenzoic acid（H2oba） and phthalic acid（H2pht）. The crystal structures of the resulting compounds, namely {[Cu（BIDPT）（oba）]·H2O}n（1） and {Cu（BIDPT）（pht）}n（2）, have been determined by single-crystal X-ray diffraction analysis. Compound 1 is of orthorhombic system, space group Pbcn with a = 27.8310（3）, b = 10.7791（1）, c = 19.3913（2）A, V = 5817.0（3） ？3 and Mr = 656.15. Compound 2 belongs to the monoclinic system, space group C2/c with a = 18.2678（2）, b = 11.0259（1）, c = 22.906（2） A, β = 97.727（2）o, V = 4571.8（8） A3 and Mr = 545.04. Structural analyses reveal that compounds 1 and 2 respectively exhibit two-dimensional（2D） wavy and corrugated layer structures. Through intermolecular hydrogen bonding, compound 1 is assembled into a 3D supramolecular structure. The thermal stability and ultraviolet spectroscopy properties of the two compounds are also investigated.

Syntheses,Crystal Structures and Luminescent Properties of Two New Zinc(Ⅱ) Complexes Based on Bifunctional Ligand

By using solvothermal method,two novel coordination polymers based on 4-（4-carboxyphen-yl）-1,2,4-triazole（Hcpt） and Zn（Ⅱ） cations,[Zn（cpt）（OH）]_n·n H_2O（FJU-32） and [Zn（cpt）（atrz）]n（FJU-33）（Hatrz = 3-amino-1,2,4-triazolate）,were synthesized and characterized by single-crystal X-ray diffraction analyses,elemental analyses,FT-IR and powder X-ray diffraction. FJU-32 crystallizes in monoclinic,space group P21/c with a = 3.7441（3）,b = 23.0384（19）,c = 11.8562（10） ？,β = 99.069（8）o,V = 1009.91（15） ？3,Dc = 1.898 g/cm3,C_9H_9N_3O_4Zn,Mr = 288.57,F（000） = 916,μ（MoKα） = 2.439 mm^（-1）,Z = 4,R = 0.0600 and wR = 0.1306 for 2412 observed reflections（I 〉 2σ（I））,and R = 0.0704 and wR = 0.1349 for all data. FJU-33 crystallizes in monoclinic space group P21/c with a = 12.7483（5）,b = 9.9922（3）,c = 9.8403（3） ？,β = 100.756（4）°,V = 1231.47（7） ？~3,Dc = 1.816 g/cm^3,C_（11）H_9N_7O_2Zn,Mr = 336.62,F（000） = 680,μ（Cu Kα） = 2.957 mm^（-1）,Z = 4,R = 0.0478 and w R = 0.1184 for 2466 observed reflections（I 〉 2σ（I））,and R = 0.0687 and w R = 0.1309 for all data. In FJU-32,Zn（Ⅱ） is coordinated to three μ3-OH groups forming an unprecedented 1D zigzag-like double chain,and the 1D double chains are connected to four neighbouring double chains by the cpt ligands to form an extended 3D porous coordination polymer. In FJU-33,the adjacent [Zn（atrz）] 2D layers are further connected by the cpt ligands via Zn–O coordinated bonds and neighboring interlayer hydrogen-bonding interactions to give rise to an overall 3D pillared layer structure. The neutron triazole group of the cpt ligand has weaker coordination ability than the triazolate anion of atrz ligand. Furthermore,FJU-32 and FJU-33 display high thermal stability up to 300 ℃,and the solid state fluorescence reveals that two new complexes are potential optical materials.

The synthesis and structural studies of mixed ligand complex,tris(1-phenyl-3-methyl-4-trifluoroacetylpyrazol-5-one)mono(1-phenyl-3-methyl-pyrazol5-one)neodymium(Ⅲ)monohydrate

A mixed ligand neodymium complex containing 1-phenyl-3-methyl-4-trifluoroacetyl- pyrazol-5-one(HPMTFP)and 1-phenyl-3-methyl-pyrazol-5-one(PMP),with molecular formula Nd(PMTFP)_3·PMP·H_2O was synthesized.Its crystal and molecular structure has been determined by single crystal X-ray diffraction method.The complex crystallizes in monoclinic system with space group C_2~5h-P2_(1/n).There are four formula units in a cell of dimensions a=12.837(3),b=23.763(5),c=16.810(4) ,β=109.58(2)°.The structure has been refined by full-matrix least-squares techniques to a final R value of 0.0487 and Rw value of 0.432.The neodymium atom is coordinated to eight oxygen atoms with the average Nd-O bond length 2.439,Its thermostability,and mass spectrum have been discussed.

Spiro(phosphoamidite) ligand(SIPHOS)/Cu(OTf)2-catalyzed highly regio-and stereo-selective hydroborations of internal alkynes with diborane in water

The highly regio-and stereoselective hydroborations of unactivated internal alkynes with diboron compound catalyzed by Cu（OTf）2 with spiro（phosphoamidite） as ligand in the presence of Cs2CO3 in water was developed.This protocol was applied efficiently in the aqueous synthesis of multi-substituted vinylboranes.

One inorganic–organic hybrid derived from reduced molybdophosphate and trinuclear cadmium(II) fragment

One new polyoxometalate （POM）-based inorganic-organic hybrid [Cdn3~HPO4）（Hbpp）（H20）2]{CdII[P4_ Mo6028H3.s（OH）312}.（H4tpb）.7H20 （1） （bpp = 1,3-bis-（4-pyridyl）propane, tpb = 1,2,4,5-tetra（4-pyridyl）- benzene） constructed from reduced molybdophosphate [P4Mo6028H3.5（OH）3]s＇5- （P4Mo6）, trinuclear Cdn-phosphate-Hbpp fragment and protonated tpb has been hydrothermally synthesized and structurally characterized by IR, elemental analyses and single crystal X-ray diffraction. The complex 1 crystallizes in the monoclinic system with the space group P21]c and cell parameters of a=15.672（12）A, b=23.839（19）A, c=27.654（2）,~, fl=115.850（10）~, V=9297.9（12） ~3, Z=4, R1 ~0.0534 and wR2 ~0.1135. In complex 1, the P4Mo6 units are bridged by CdII ions to form the classic sandwich-type [Cd（P4Mo6）2] dimers, which are further connected into a two dimensional network via the trinuclear Cdn subunits. The tpb is synthesized in situ from the bpp ligands and connects the adjacent 2D layers into a 3D supramolecular framework through hydrogen bonding interactions. The electrochemical and fluorescent properties of complex 1 have been investigated.