Crystal Structures and Phosphorescent Properties of Group 14 Dipyridinometalloles and Their Copper Complexes. Issue 8 (26th August 2020)

• Record Type: Journal Article
• Authors: Ohshita, Joji; Yamaji, Kosuke; Adachi, Yohei
• Is Part Of: ChemPlusChem. Volume 85:Issue 8(2020)
• Page Start: 1912
• Page End: 1918
• Publication Date: 2020-08-26
• Subjects: coordination chemistry -- copper -- Group 14 elements -- metalloles -- phosphorescence; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/cplu.202000418
• Languages: English
• ISSNs: 2192-6506

Abstract

Abstract: We recently reported dipyridinosilole (DPyS) and dipyridinogermole (DPyG) as π‐conjugated units that show low‐temperature phosphorescence. A copper complex of DPyG 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. Abstract : Tin is in :Diphenyldipyridinostannole (DPySn1) was prepared and its optical and electrochemical properties were investigated in comparison with those of its silole and germole congeners (DPyS1 and DPyG1). Of these, DPySn1 showed the most red‐shifted phosphorescence at 77 K in the solid state. The solid‐state room temperature phosphorescence and crystal structures of copper complexes of these dipyridinometalloles were also investigated, and showed clear dependence on the metallole element.