Abstract: | Copper (II) complexes [Cu(dmit)(phen)]2 (1) and [Cu(mnt)(phen)] n (2) (mnt2??=?maleonitriledithiolate, dmit2??=?1,3-dithiole-2-thione-4,5-dithiolate, phen?=?1,10-phenanthroline) have been prepared by ligand-exchange between phen and [N(Bu)4]2[Cu(dmit)2] or [N(Bu)4]2[Cu(mnt)2]. Both complexes have been characterized by spectroscopic, electrochemical, and single-crystal X-ray analysis. In complex 1, dimers are extended into a two-dimensional array by weak S5–Cu contacts. In complex 2, monomers are extended into chains in a head-to-tail arrangement by weak Cu–S coordination bonds and π–π stacking interactions. |