通过X射线粉末衍射法测定纯配体金（I）、银（I）和铜（I）芳基/烷基乙炔基配位聚合物的结构

Structure determination of homoleptic AuI, AgI, and CuI aryl/alkylethynyl coordination polymers by X-ray powder diffraction.

作者信息

Chui Stephen S Y, Ng Miro F Y, Che Chi-Ming

机构信息

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.

出版信息

Chemistry. 2005 Mar 4;11(6):1739-49. doi: 10.1002/chem.200400881.

DOI:10.1002/chem.200400881

PMID:15669067

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.

摘要

本文描述了通过X射线单晶和粉末衍射对五种同配体d(10)金属-芳基/烷基乙炔化物[RC≡CM]（M = Cu，R = tBu 1，nPr 2，Ph 3；R = Ph，M = Ag 4；Au 5）进行结构测定的过程。配合物1·C6H6呈现出一种不寻常的Cu20连环簇结构，具有多种类型的tBuC≡C→Cu配位模式。以该单晶结构作为后续对X射线粉末衍射数据进行Rietveld精修的起始模型，发现由CuI和tBuC≡CH合成的粉末结构与1相同。配合物2具有由通过桥连的nPrC≡C基团连接的离散之字形Cu4亚基组成的扩展片状结构。配合物3形成具有扩展的Cu-Cu梯状结构（Cu-Cu = 2.49(4)-2.83(2) Å）的无限链结构。银(I)同系物4与3同构（平均Ag-Ag距离为3.11 Å），而金(I)类似物5形成具有PhC≡C柱的Au...Au蜂窝状网络（Au-Au = 2.98(1)-3.26(1) Å）。在已确定的结构背景下，讨论了这些聚合物体系的固态性质，包括光致发光、ν(C≡C)伸缩频率和热稳定性。