两种含醛基的铱配合物用于半胱氨酸和OH-的识别
Two Iridium Complexes Containing Aldehyde Group for Cysteine and OH- Recognition
作者单位E-mail
佟鑫 河北工业大学化工学院, 天津 300130  
赵世盛 河北工业大学化工学院, 天津 300130  
楚曦 河北工业大学化工学院, 天津 300130  
李文豪 河北工业大学化工学院, 天津 300130  
李红岩 河北工业大学化工学院, 天津 300130 hyli@hebut.edu.cn 
摘要: 以4,4'-二溴-2,2'-联吡啶(dbr-bpy)为中性配体,分别以6-苯基烟醛(L1)、6-(4-三氟甲基苯基)吡啶-3-甲醛(L2)为环金属配体合成了2种Ir (Ⅲ)配合物[Ir (L1)2(dbr-bpy)]PF6Ir1)和[Ir (L2)2(dbr-bpy)]PF6Ir2),并通过核磁共振波谱和质谱对其结构进行了表征。在乙腈溶液中配合物Ir1Ir2的发射波长分别为584和530 nm,发光量子效率分别为49%和66%。电化学测试和理论计算表明,环金属配体中CF3的引入,可以降低最高占据分子轨道(HOMO)的能级,从而使氧化电位向正极移动。配合物Ir1Ir2与半胱氨酸(Cys)均以1∶2的比例结合,发生磷光猝灭响应,同时表现出良好的抗干扰能力,检出限分别为35.1和18.5 μmol· L-1。将OH-加入配合物Ir2的DMSO/H2O (7∶3,V/V)溶液中,OH-取代配合物中性配体上的溴取代基,使配合物Ir2的发射峰蓝移,溶液发光颜色由黄色变为绿色,发光强度提升4倍。
关键词: 铱配合物  半胱氨酸  醛基  识别OH-
基金项目: 河北省自然科学基金(No.B2022202060)资助
Abstract: Two iridium(Ⅲ) complexes,[Ir(L1)2(dbr-bpy)]PF6 (Ir1) and[Ir(L2)2(dbr-bpy)]PF6 (Ir2) with 4, 4'-dibromo-2, 2'-bipyridine (dbr-bpy) as neutral ligand, 6-phenylnicotinaldehyde (L1) and 6-(4-trifluoromethylphenyl)pyridine-3-carbaldehyde (L2) as cyclometalated ligands, were synthesized and characterized by 1H NMR, 13C NMR, IR and MS spectra. For the emission spectra in acetonitrile solution, the maximum peaks were located at 584 and 530 nm for complexes Ir1 and Ir2 with quantum efficiencies of 49% and 66%, respectively. The introduction of electronwithdrawing trifluoromethyl and aldehyde groups resulted in an obvious blue shift in the emission spectra of complexes Ir1 and Ir2. The study of cyclic voltammograms indicates trifluoromethyl moieties in the cyclometalated ligands of complexes Ir1 and Ir2 can reduce the energy of the highest occupied molecular orbital (HOMO), and make the oxidation potential shift towards the anode. Density functional theory (DFT) calculations have been carried out to gain insight into their frontier molecular orbital properties and transition details. Complexes Ir1 and Ir2 displayed significant phosphorescence quenching upon binding to cysteine (Cys), and the binding stoichiometry was approximately 1:2 with the detection limit of 35.1 and 18.5 μmol·L-1, respectively. Both complexes showed a good anti-interference ability for the detection of Cys. Upon the addition of OH- into the solution of Ir2 in DMSO/H2O (7:3, V/V), OH- replaced the bromine substituents on the neutral ligand of Ir2, resulting in a blue shift of the emission peak. The luminescence color of complex Ir2 changed from yellow to green and Ir2 showed a 4-fold enhanced emission in an alkaline environment when compared to neutral pH. In addition, complex Ir2 exhibited high sensitivity and selectivity for OH- and showed good anti-interference ability.
Keywords: iridium complex  cysteine  aldehyde group  OH- sensing
投稿时间:2022-01-25 修订日期:2022-07-10
摘要点击次数:  2816
全文下载次数:  334
佟鑫,赵世盛,楚曦,李文豪,李红岩.两种含醛基的铱配合物用于半胱氨酸和OH-的识别[J].无机化学学报,2022,38(10):1939-1947.
查看全文  查看/发表评论  下载PDF阅读器
Support information: 相关附件:   220038_220038-Supporting_Information.doc