title: Structure determination of homoleptic AuI, AgI, and CuI aryl/alkylethynyl coordination polymers by X-ray powder diffraction.
abstract: This article describes the structure determination of five homoleptic d(10) metal-aryl/alkylacetylides [RC triple bond 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.C6H6 reveals an unusual Cu20 catenane cluster structure that has various types of tBuC triple bond 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 triple bond CH was found to have the same structure as 1. Complex 2 has an extended sheet structure consisting of discrete zig-zag Cu4 subunits connected through bridging nPrC triple bond 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 triple bond C pillars (Au-Au=2.98(1)-3.26(1) A). Solid-state properties including photoluminescence, nu(C triple bond C) stretching frequencies and thermal stability of these polymeric systems are discussed in the context of the determined structures.
authors.affiliation: Department of Chemistry, HKU-CAS Joint Laboratory of New Materials and Open Laboratory of Chemical Biology of Institute of Molecular Technology for Drug Discovery and Synthesis, University of Hong Kong, China.
authors.forename: Stephen S Y
authors.initials: SS
authors.lastname: Chui
authors.forename: Miro F Y
authors.initials: MF
authors.lastname: Ng
authors.forename: Chi-Ming
authors.initials: CM
authors.lastname: Che
mesh_terms: D000114:Acetylene / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D006046:Gold / Q000737:chemistry*; D008024:Ligands; D049449:Luminescence; D008958:Models, Molecular; D009942:Organometallic Compounds / Q000737:chemistry*; D010777:Photochemistry; D011108:Polymers / Q000737:chemistry*; D033362:Powder Diffraction; D012680:Sensitivity and Specificity; D012834:Silver / Q000737:chemistry*; D017550:Spectroscopy, Fourier Transform Infrared
chemical_list: D008024:Ligands; D009942:Organometallic Compounds; D011108:Polymers; D012834:Silver; D006046:Gold; D003300:Copper; D000114:Acetylene