Phosphorescent vaporchromism of manganese(II) complexes of 1,3-bis(diphenylphosphinoxy) propane

Abstract

Manganese (II) complexes of 1,3-bis(diphenylphosphinoxy) propane (DPPPO2), [Mn(DPPPO2)Br2] n ( 1G ) and [Mn2(DPPPO2)4Br2]Br2•4CH3OH ( 1R ), were synthesized. The structures of them were determined by X-ray single crystal diffraction. 1G exhibits a one-dimensional chain structure, whereas 1R is a cyclic binuclear complex. The tetrahedrally coordinated complex 1G exhibits green emission ( λ em= 514 nm) under UV light irradiation, while binuclear complex 1R with distorted square pyramidal geometry gives red emission ( λ em= 634 nm). When 1G is exposed to methanol vapor, the structure is rearranged to 1R , accompanied by a drastic red shift of phosphorescent emission band. The maximum emission peak shifts from 514 to 634 nm with the green emission converted to red one. On the other hand, upon heated to 150 ° C, 1R is converted to 1G with red luminescence converted to green one. X-ray diffraction experiments show that 1G is converted to 1R upon exposure to methanol vapor, but upon heated at 150 ° C, 1R can be reverted to 1G , thereby realizing a reversible interconversion between 1G and 1R .