Synthesis and Crystal Structure of a Tetranuclear Silver Complex with Bis(diphenylphosphino) amine-dioxide as a Tridentate Ligand

The tetranuclear complex[Ag4（μ-Ph2PNHPPh2）2（μ-OPh2PNPPh2O）2] （PF6）2·CH3COCH3 containing bis（diphenylphosphino）amine （Ph2PNHPPh2） and deprotonated bis- （diphenylphosphino）amine-dioxide （OPh2PNPPh2O） was isolated and characterized by X-ray crystallography. The deprotonated OPh2PNPPh2O acts as a tridentate ligand in a chelating and bridging mode. Two of the four Ag atoms are in a trigonal planar environment composed of PO2 chromophore, whereas the other two are coordinated with PN donors in a distorted linear arrangement. The title complex （C51H47Ag2F6N2O3P5） crystallizes in triclinic, space group P1^- with a = 12.9552 （2）, b = 14.1691（3）, c = 15.8110（3）A°, α = 68.7500（10）, β= 86.8840（10）, γ = 75.6170（10）°, V= 2618.16 （8） A°^3, Mr= 1220.50, Z = 2, Dc= 1.548 g/cm^3, F（000） = 1228 and μ（MoKα） = 0.965 mm^-1. The final refinements converged at R = 0.0679 and wR = 0.1528 for 7001 observed reflections （I〉 2σ（I））.

Coordination Triangular Prism of Bisilver Complex with Triply-bridged of Bis(diphenylphosphino)amine

The binuclear complex [Ag2(m-Ph2PNHPPh2)3](ClO4)2CH2Cl2CH3OH (Ph2PNHP- Ph2 = bis(diphenylphosphino)amine) was prepared from the reaction of AgClO4 with bis- (diphenylphosphino)amine in equimolar ratio through self-assembly. The coordination cation affords a triply-bridging [Ag2L3]-type coordination moiety. The silver atom is in a trigonal planar environment with P3 coordination chromophore. The complex (C74H69Cl4N3O9P6Ag2) crystallizes in monoclinic, space group Cc with a = 18.3738(1), b = 20.0207(4), c = 20.5422(4) ? b = 95.829(1), V = 7517.5(2) 3, Z = 4, Mr = 1687.68, Dc = 1.491 g/cm3, F(000) = 3432, m = 0.848 mm-1, the final R = 0.0460 and wR = 0.0935 for 7005 observed reflections with I > 2s(I).

Structure and Thermochromic Property of a Silver(I) Complex Based on Dicyanamide and Phosphine Ligands

A new silver(I)complex{Ag2(dppm)2[N(CN)2]}2[μ-N(CN)2]2(1)with chelate ligand bis(diphenylphosphino)methane(dppm)and bridging ligand dicyanamide(N(CN)2)was carefully synthesized and fully characterized by single-crystal X-ray crystallography,IR spectrometry,high-resolution mass spectrometry,thermal analysis and 1H NMR.According to the crystal structure analysis,this complex could be considered as two binucleate moieties{Ag2(dppm)2[N(CN)2]}+linked by two bridging anionic ligands N(CN)2-.It exhibits thermochromic property in solid state.The dependence of color or emission of substance on temperature is known as thermochromism.Various temperature luminescences of complex 1 are tested.Along with the reduction of temperature from 298 K to 77 K,a noticeable emission enhancement as well as lifetime extension is observed.

Silver(Ⅰ)Complexes with Mixed Diphosphine Ligands:Syntheses,Characterization and Spectroscopic Properties

Two novel silver（I） complexes [Ag（DPEphos）（dppe）]Cl O4（1） and [Ag（DPEphos）-（dppe）]SCN（2）（DPEphos = bis[2-（diphenylphosphino）phenyl]ether, dppe = bis（diphenylphosphino）ethane） are synthesized and characterized by IR, 1H/31 P NMR spectroscopy and fluorescence spectra. Complex 1 crystallizes in monoclinic, space group P21/c with a = 14.8821（12）, b = 12.6620（11）, c = 36.025（3） ？, β = 112.633（2）°, V = 6265.7（9） ？3, C62H52 Cl O5P4Ag, Mr = 1144.24, Z = 4, Dc = 1.213 g/cm3, F（000） = 2352, μ = 0.510 mm-1, the final R = 0.0616 and w R = 0.1192 for 4003 observed reflections（I 〉 2σ（I））. Complex 2 crystallizes in monoclinic, space group P21/c with a = 14.9021（13）, b = 12.6100（11）, c = 35.920（3） A, β = 112.852（2）°, V = 6220.2（9） A3, C63H52NOP4 SAg, Mr = 1102.87, Z = 4, Dc = 1.178 g/cm3, F（000） = 2272, μ = 0.498 mm-1, the final R = 0.0912 and w R = 0.1706 for 3287 observed reflections（I 〉 2σ（I））. In mono-nuclear complexes 1 and 2, the Ag（I） atom is chelated by DPEphos and dppe ligand. In the 31 P NMR spectra, there are splitting signals（doublets or triplets） which can be attributed to the coupling of the 107,109Ag–31P（from DPEphos or dppe ligand）. All the emission peaks of these complexes are attributed to ligand-centered（π-π＊） transitions.