新型双核配合物的形成及荧光性质研究

利用光谱学方法研究了Ru(bpy)2TPPHZ]2+(TPPHZ=四吡啶3,2-a: 2',3'-c: 3",2"-h: 2'",3'"-j]吩嗪)和Ru(bpy)2ODHIP]2+(ODHIP=3,4-二羟基-咪唑并4,5-f]1,10]邻菲咯啉)与Ni2+的配位情况及配位后的荧光性质变化, 探讨了配合物与Ni2+配位形成双核配合物后与DNA的作用机制变化. 结果表明, Ru(bpy)2TPPHZ]2+和Ru(bpy)2ODHIP]2+均可与Ni2+配位, 形成双核配合物Ru(bpy)2(TPPHZ)Ni]4+和Ru(bpy)2(ODHIP)Ni]4+, 配合物的荧光强度随着Ni2+浓度的增加而减弱. 与DNA作用后, 配合物仍可与Ni2+配位形成双核配合物, Ru(bpy)2(TPPHZ)Ni]4+的荧光几乎完全消失, 同时配合物与DNA保持插入模式作用, 而配合物Ru(bpy)2(ODHIP)Ni]4+与DNA的作用则由沟面结合改为插入结合, 同时配合物的荧光减弱.

Formation and Luminescent Properties of New Heterobimetallic Complexes

The formation of new heterobimetallic complexes obtained via the coordination reactions of Ru(bpy)2TPPHZ]2+(TPPHZ=tetrapyrido3,2-a: 2',3'-c: 3",2"-h: 2'",3'"-j]phenazine) and Ru(bpy)2ODHIP]2+(ODHIP=3,4-dihydroxyl-imidazo4,5-f]1,10]phenanthroline) with Ni2+ were investigated by spectroscopic methods. The DNA-binding and luminescent properties of the complexes after coordinating with Ni2+ were also studied. The experimental results indicate that both Ru(bpy)2TPPHZ]2+ and Ru(bpy)2ODHIP]2+ could coordinate with Ni2+ to form the heterobimetallic complexes Ru(bpy)2•(TPPHZ)Ni]4+ and Ru(bpy)2(ODHIP)Ni]4+. The emission intensity of the complexes decreased with increasing the amounts of Ni2+. After binding to DNA, both complexes could coordinate with Ni2+ to form the heterobimetallic complexes. Ru(bpy)2(TPPHZ)Ni]4+ kept binding to DNA by intercalation, and the luminescence of complex almost disappeared at n(Ni)/n(Ru)=1. While the binding mode of Ru(bpy)2•(ODHIP)Ni]4+ changed from groove binding to intercalation, and the emission intensity of the complex decreased.