Synthesis and Characterization of Copper(I) Halide Complexes Prepared with Bipodal Diacylthioureas

Bipodal diacylthioureas [MesC(O)NHC(S)NH] 2 R (R = C 6 H 4 ‐1,2 ( L 1 , 1 ), C 6 H 4 ‐1,4 ( L 2 , 2 )) were synthesized, and their complexation reactions with equimolar Cu(I) halides CuX (X = Cl, Br, ) were investigated. The obtained ligands L 1–2 and the resultant Cu(I) complexes ( 3 – 8 ) were characterized by FT‐IR, 1 H NMR, 13 C NMR spectroscopy, elemental analysis and single‐crystal X‐ray diffraction. The complexation of L 1 with CuX gave three different 1D polymers: the infinite single chain ( L 1 CuCl) n ( 3 ), edge‐shared double‐ring chain {[( µ ‐ L 1 )CuBr] 2 } n ( 4 ), and vertex‐shared double‐ring chain {[ L 1 Cu( µ ‐I)] 2 } n ( 5 ). Similarly, but more pronounced, the treatment of L 2 with CuX resulted in the formation of 1D edge‐shared double‐ring chain {[( µ ‐ L 2 )CuCl] 2 } n ( 6 ), 0D discrete dinuclear metallamacrocyclic ring ( L 2 CuBr) 2 ( 7 ), and 3D network polymer [ L 2 Cu( µ ‐I)] n ( 8 ), respectively. The structural diversity may be related to the suitable spacer, flexible C=S directionality and binding roles of halide anions and sulfur donors. Among Cu(I) complexes ( 3 – 8 ) as prepared, both chloride (in 3 and 6 ) and bromide anions (in 4 and 7 ) acted as terminal ligands, while the iodide anions (in 5 and 8 ) served as bridging ligand. In contrast, only in edge‐shared double‐ring chains ( 4 and 6 ) it was found that the sulfur donors (one of two in each L n ) played as the bridging ligand.