Copper(I) Coordination Polymers with Alkanedithiol and ‐dinitrile Bridging Ligands

Abstract

AbstractCuI‐based coordination polymers with 1, 2‐ethanedithiol, 3, 6‐dioxa‐1, 8‐octanedithiol and 3‐oxa‐1, 5‐pentanedinitrile as respectively μ‐S, S′ and μ‐N, N′ bridging ligands have been prepared by reaction of CuI with the appropriate alkane derivative in acetonitrile. [Cu(HSCH2CH2SH)2]I (1) contains 44 cationic nets, [(CuI)2(HSCH2CH2OCH2CH2OCH2CH2SH)] (2) neutral layers in which stairlike CuI double chains are linked by dithiol spacers. In contrast to these 2D polymers, [CuI(NCCH2CH2OCH2CH2CN)] (3) and [(CuI)4(NCCH2CH2OCH2CH2CN)2] (4) both contain infinite chains with respectively (CuI)2 rings and distorted (CuI)4 cubes as building units. Solvothermal reaction of CuI with the thiacrown ether 1, 4, 10‐trithia‐15‐crown‐5 (1, 4, 10TT15C5) in acetonitrile affords the lamellar coordination polymer [(CuI)3(1, 4, 10TT15C5)] (7) in which copper atoms of individual CuI double chains are bridged in a μ‐S1, S4 manner. The third sulphur atom S10 of the thiacrown ether coordinates a copper(I) atom from a parallel chain to generate a 2D network.