1,3-Dithiolane and 1,3-Ferrocenyl-dithiolane as Assembling Ligands for the Construction of Cu(I) Clusters and Coordination Polymers
Résumé
The parent compound 1,3-dithiolane L1 reacts with CuI providing the 2D coordination polymer (CP) [{Cu(μ2-I)2Cu}(μ2-L1)2] n (CP1). The Cu⋯Cu distance within the Cu(μ2-I)2Cu rhomboid is temperature-dependent and shrinks from 2.9081(7) (294 K) to 2.8743(5) (100 K). The 1D polymeric compound [{Cu(μ2-Br)}(μ2-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(μ2-Cl)}(μ2-L1)] n (CP3). In contrast to CP1 incorporating dinuclear Cu(μ2-I)2Cu units as connection nodes, the isolated Cu atoms of CP2 and CP3 are bridged by a single μ2-Br or μ2-Cl ligand giving rise to infinite [Cu(μ2-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 [{Cu2(μ4-I)(μ2-I)}(μ2-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 [{Cu4(μ2-Br)2(μ3-Br)2}(μ2-L2)2(MeCN)2] (CL1) is formed.
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