环2-(4-三氟甲基)苯基吡啶钌亚硝酰配合物的合成与光敏NO释放  

Synthesis and photosensitive release of NO of the cycloruthenated 2-(4-trifluoromethyl)phenylpyridine nitrosyl

作　　者：李襄宏[1] 吴秋俣 王艺荣 李珍 LI Xianghong;WU Qiuyu;WANG Yirong;LI Zhen(School of Chemistry and Materials Science,South-Central Minzhu University,Wuhan 430074,China)

机构地区：[1]中南民族大学化学与材料科学学院,武汉430074

出　　处：《中南民族大学学报（自然科学版）》2024年第1期8-15,共8页Journal of South-Central University for Nationalities：Natural Science Edition

基　　金：国家自然科学基金资助项目(21971258)。

摘　　要：由环金属钌配合物[Ru(bpy)_(2)(4-CF3ppy)]PF_(6)(bpy=2,2′-二联吡啶,4-CF_(3)Hppy=2-(4-三氟甲基)苯基吡啶))合成了一个新的钌亚硝酰配合物[Ru(bpy)(4-CF_(3)ppy)(CH_(3)CN)NO](PF_(6))_(2)(配合物1),并通过NMR、MS和IR表征确认其结构.结果表明:配合物1中属于NO^(+)特征伸缩振动峰出现在1911 cm^(-1)处,并在电化学中呈现显著的Ru^(Ⅱ)NO+→Ru^(Ⅱ)NO·和Ru^(Ⅱ)NO·→Ru^(Ⅱ)NO-两步连续还原过程,表明其中存在Ru^(Ⅱ)-NO+.此外,光照下吸收光谱的显著变化显示了该配合物光敏NO释放的可能性,并由EPR光谱确认.通过Griess试剂测定发现:因─CF_(3)引入,配合物1的光敏NO释放量明显高于[Ru(bpy)(ppy)(CH_(3)CN)NO]^(2+)和[Ru(bpy)(4-OCH_(3)ppy)(CH3CN)NO]^(2+),这一结果与模拟计算的Ru核与NO^(+)的结合能大小一致.故吸电子基团的引入更有利于Ru^(Ⅱ)-NO^(+)的NO光敏释放,配合物1可作为光敏NO供体.Starting the cycloruthenated complex[Ru(bpy)_(2)(4-CF_(3)Hppy)]PF_(6)(bpy=2,2′-bipyridine,4-CF_(3)ppy=2-(4-trifluoromethyl)phenylpyridine)),a new ruthenium(Ⅱ)nitrosyl complex[Ru(bpy)(4-CF_(3)ppy)(CH_(3)CN)NO](PF_(6))_(2)(complex 1)was synthesized and characterized by NMR,MS,and IR.The characteristic NO^(+)stretching vibration at 1911 cm^(-1) and two significant continuous reduction steps of Ru^(Ⅱ)NO+→Ru^(Ⅱ)NO·and Ru^(Ⅱ)NO·→Ru^(Ⅱ)NO^(-) in electrochemistry were observed,proving the presence of Ru^(Ⅱ)-NO^(+).In addition,the dramatic absorption spectral changes under irradiation indicated the possible photo-release of NO,which was further confirmed by EPR spectra.Through the Griess reagent determination,the photosensitive NO release of complex 1 was found significantly higher than those of[Ru(bpy)(ppy)(CH_(3)CN)NO]^(2+)and[Ru(bpy)(4-OCH_(3)ppy)(CH_(3)CN)NO]^(2+),due to the introduction of─CF_(3).The results was consistent with the simulated binding energy between Ru core and nitrosyl.The introduction of electron-withdrawing groups is therefore more conducive to the photosensitive release of NO from Ru^(Ⅱ)-NO^(+),enabling complex 1 to serve as a photosensitive NO-donor.

关 键 词：钌亚硝酰配合物 环金属钌配合物 NO分子供体 光敏释放 

分 类 号：O614.821[理学—无机化学]