1,3-双(二苯基膦氧)丙烷锰(Ⅱ)配合物磷光蒸气变色研究

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

本文以1,3-双(二苯基膦氧)丙烷(DPPPO2)为配体,合成了两种不同结构的锰(Ⅱ)配合物,其化学式分别为[Mn(DPPPO2)Br2]n(1G)和[Mn2(DPPPO2)4Br2]Br2·4CH3OH(1R).通过X射线单晶衍射确定了这两个化合物的结构.1G呈现一维链状结构,1R则为笼状结构的双核配合物.四面体构型的Mn(Ⅱ)化合物1G在紫外灯照射下呈现绿光发射(λem=514 nm),而扭曲四方锥构型的Mn(Ⅱ)化合物1R呈现红光发射(λem=634 nm).无论是晶体、粉末还是PMMA掺杂薄膜,1G暴露在甲醇蒸气中可发生结构重排,转化为1R,伴随磷光发射光谱显著红移,最大发射峰从514 nm红移到634 nm,同时绿光转变为红光发射.另一方面,若150℃加热1R,则转化为1G,伴随着红光转换为绿光发射.X射线衍射实验表明,化合物1G吸收甲醇蒸气后转变为1R,但加热到150℃时1R又可以恢复到1G,由此实现1G与1R可逆转化.

Manganese(II)complexes of 1,3-bis(diphenylphosphinoxy)propane(DPPPO2),[Mn(DPPPO2)Br2]n(1 G)and[Mn2(DPPPO2)4 Br2]Br2·4 CH3 OH(1 R),were synthesized.The structures of them were determined by X-ray single crystal diffraction.1 G exhibits a one-dimensional chain structure,whereas 1 R is a cyclic binuclear complex.The tetrahedrally coordinated complex 1 G exhibits green emission(λem=514 nm)under UV light irradiation,while binuclear complex 1 R with distorted square pyramidal geometry gives red emission(λem=634 nm).When 1 G is exposed to methanol vapor,the structure is rearranged to 1 R,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,1 R is converted to 1 G with red luminescence converted to green one.X-ray diffraction experiments show that 1 G is converted to 1 R upon exposure to methanol vapor,but upon heated at 150°C,1 R can be reverted to 1 G,thereby realizing a reversible interconversion between 1 G and 1 R.