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 [ Cu 4 I ( iso - abt ) 2 ] 4 DMF · 4 MeCN ( 1 ) containing the tetranuclear electroneutral complex [ Cu 4 I ( iso - abt ) 2 ] ( 2 ) is formed by the reaction of CuI in acetonitrilic solution and recrystallization from DMF, whereas [ Cu 12 I ( iso - abt ) 6 ] [ Et 3 NH ] 2 [ BF 4 ] 2 · 9 MeCN ( 3 ) containing dodecanuclear [ Cu 12 I ( 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.