From the {Cu(μ2-S)N}4 butterfly architecture to the {Cu(μ3-S)N}12 double wheel

Copper(I) complexes with {Cu(μ2-S)N}4 and {Cu(μ3-S)N}12 core portions of butterfly-shaped or double wheel architectures have been isolated in the reaction of Cu(I) with the Schiff base ligand C6H4(CHNC6H4S)2, “iso-abt  ”, under different conditions. 3[Cu4I(iso-abt)2]4DMF·4MeCN(1) containing the tetranuclear electroneutral complex [Cu4I(iso-abt)2](2) is formed by the reaction of CuI in acetonitrilic solution and recrystallization from DMF, whereas [Cu12I(iso-abt)6][Et3NH]2[BF4]2·9MeCN(3) containing dodecanuclear [Cu12I(iso-abt)6](4) wheels is accessible starting from CuBF4. Complexes 2 and 4 represent the first examples of cyclic complexes with the same overall stoichiometry but different ring sizes. The ligand induces two different coordination environments around copper(I) by switching between μ2- and μ3-sulfur bridging modes.

Graphical abstractThe copper(I) complexes Cu4[C6H4(CHNC6H4S)2]2 (2) and Cu12[C6H4(CHNC6H4S)2]6 (4) with butterfly-shaped Cu(μ2-S)N4 and double-wheel-like Cu(μ3-S)N12 cores, respectively, are the first examples wherein the ligand induces two different coordination environments around Cu(I) by switching between μ2- and μ3-sulphur bridging modes.Figure optionsDownload full-size imageDownload as PowerPoint slide