1,3-Dithiolane and 1,3-Ferrocenyl-dithiolane as Assembling Ligands for the Construction of Cu(I) Clusters and Coordination Polymers

The parent compound 1,3-dithiolane L1 reacts with CuI providing the 2D coordination polymer (CP) [{Cu(mu(2)-I)(2)Cu}(mu(2)-L1)(2)] (n) (CP1). The Cu center dot center dot center dot Cu distance within the Cu(mu(2)-I)(2)Cu rhomboid is temperature-dependent and shrinks from 2.9081(7) (294 K) to 2.8743(5) (100 K). The 1D polymeric compound [{Cu(mu(2)-Br)}(mu(2)-L1)] (n) (CP2) was isolated upon treatment of CuBr with L1 in MeCN solution. Likewise, treatment of L1 with CuCl in a 1:1 ratio results in formation of the unusual 1D CP [{Cu(mu(2)-Cl)}(mu(2)-L1)] (n) (CP3). In contrast to CP1 incorporating dinuclear Cu(mu(2)-I)(2)Cu units as connection nodes, the isolated Cu atoms of CP2 and CP3 are bridged by a single mu(2)-Br or mu(2)-Cl ligand giving rise to infinite [Cu(mu(2)-X)Cu] (n) ribbons. Reaction of ferrocenecarbaldehyde with 1,2-ethanedithiol affords the crystallographically characterized ferrocenyl-dithiolane Fc-C(H)S2C2H4 (L2). L2 was used as organometallic dithioether ligand to assemble, upon treatment with CuI, the original luminescent 1D CP [{Cu-2(mu(4)-I)(mu(2)-I)}(mu(2)-L2)] (n) (CP4), in which both S atoms of one L2 molecule span two copper centers of a meander-shaped infinite (CuI) (n) ribbon. Upon reaction of L2 with CuBr in a 1:2 ratio, the discrete tetranuclear cluster [{Cu-4(mu(2)-Br)(2)(mu(3)-Br)(2)}(mu(2)-L2)(2)(MeCN)(2)] (CL1) is formed.