Crystal Structures and Phosphorescent Properties of Group 14 Dipyridinometalloles and Their Copper Complexes

Chempluschem. 2020 Aug;85(8):1912-1918. doi: 10.1002/cplu.202000418.

Abstract

We recently reported dipyridinosilole (DPyS) and dipyridinogermole (DPyG) as π-conjugated units that show low-temperature phosphorescence. A copper complex of DPG shows solid-state phosphorescence at room temperature. In this work, we prepared diphenyldipyridinostannole (DPySn1). Its optical and electrochemical properties were investigated and compared with those of DPyS1 and DPyG1 with the same phenyl substituents. DPySn1 showed the most red-shifted phosphorescence at 520 nm at 77 K in the solid-state, which is likely due to the intermolecular Sn-pyridine interaction that was confirmed by single-crystal X-ray diffraction. Copper complexes of DPyS1 and DPySn1 were also prepared and it was found that the phosphorescence of these dipyridinometallole-copper complex solids was red-shifted in the order of DPySn1-Cu (617 nm)<DPyG1-Cu (624 nm)<DPyS1-Cu (645 nm). Single-crystal X-ray diffraction studies were performed for DPyS1-Cu and DPySn1-Cu complexes. DPyS1-Cu showed a double-chained polymeric ladder-like structure with Cu4 I4 cluster units and DPySn1-Cu possessed a single chain polymeric structure with Cu2 I2 units, analogous to DPyG1-Cu.

Keywords: Group 14 elements; coordination chemistry; copper; metalloles; phosphorescence.