Structure Determination of Homoleptic Au~I,Ag~I,and Cu~I Aryl/Alkylethynyl Coordination Polymers by X-ray Powder Diffraction

摘要

This article describes the structure determination of five homo-leptic d~(10) metal-aryl/alkylacetylides [RC ident to CM] (M = Cu,R = tBu 1,nPr 2,Ph 3;R = Ph,M = Ag 4;Au 5) by using X-ray single-crystal and powder diffraction.Complex 1 centre dot C_6H_6 reveals an unusual Cu_(20) catenane cluster structure that has various types of tBuC ident to C->Cu coordination modes.By using this single-crystal structure as a starting model for subsequent Rietveld refinement of X-ray powder diffraction data,the structure of the powder synthesized from CuI and tBuC ident to CH was found to have the same structure as 1.Complex 2 has an extended sheet structure consisting of discrete zig-zag Cu_4 subunits connected through bridging nPrC ident to C groups.Complex 3 forms an infinite chain structure with extended Cu-Cu ladders (Cu-Cu = 2.49(4)-2.83(2) A).The silver(I) congener 4 is iso-structural to 3 (average Ag-Ag distance 3.11 A),whereas the gold(I) analogue 5 forms a Au...Au honeycomb network with PhC ident to C pillars (Au-Au = 2.98(1)-3.26(1) A).Solid-state properties including photoluminescence,v(C ident to C) stretching frequencies and thermal stability of these polymeric systems are discussed in the context of the determined structures.