Hybrid Mn(II)–Cu(I) Complex Based on 1,3,5-Tris(diphenylphosphinyl)benzene

The reaction of 1,3,5-tris(diphenylphosphinylbenzene (L) with MnI2 in the presence of CuI (wet MeCN, 25°C, 30 min) leads to the formation of the complex [MnL4(H2O)2][Cu5I7(CH3CN)]·7MeCN with yield of 72%. The Mn2+ ion of this complex has a distorted Mn@O6 octahedral environment formed by four L ligands and two coordinated water molecules. The [Cu5I7(CH3CN)]2– anion has an unprecedented structure of the {Cu5I7} framework, which contains five copper atoms bound by bridging iodide ions (µ2, µ3, and µ4), and also four short Cu···Cu contacts (<2.80 Å). It has been shown that the synthesized complex at 298 K exhibits weak photoluminescence attributed to cluster-centered phosphorescence from the iodocuprate anion.