Yuan Qin-Zhen, Fan Qianwenhao, Lv Hang, Chen Wen-Wen, Yang Xue-Xiao, Cao Deng-Ke, Wen Jing
State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, People's Republic of China.
Hubei Key Laboratory of Plasma Chemistry and Advanced Materials, School of Materials Science and Engineering, Wuhan Institute of Technology, Wuhan 430205, People's Republic of China.
Inorg Chem. 2020 Dec 7;59(23):17071-17076. doi: 10.1021/acs.inorgchem.0c02279. Epub 2020 Nov 10.
Two anthracene-based complexes [Ir(pbt)(aip)]Cl () and [Ir(pbt)(aipm)]Cl () have been synthesized based on the ligands aip = 2-(9-anthryl)-1-imidazo[4,5-][1,10]phenanthroline, aipm = 2-(9-anthryl)-1-methyl-imidazo[4,5-][1,10]phenanthroline, and pbtH = 2-phenylbenzothiazole in order to explore both the influence of the substituent group R (R = H in and CH in ) on photo-oxidation activity and photo-oxidation-induced luminescence. Both H NMR spectra and ES mass spectra indicate that the anthracene moiety in complex can be oxidized at room temperature upon irradiation with 365 nm light. Thus, this complex shows photo-oxidation-induced turn-on yellow luminescence. Compared to , complex incorporates an R = CH group, resulting in very weak photo-oxidation activity. On the basis of experimental results and quantum chemical calculation, we report the differences between and in both photo-oxidation behavior and the related luminescence modulation and discuss the relationship between photo-oxidation activity and substituent group R in these complexes.
基于配体aip = 2-(9-蒽基)-1-咪唑并[4,5-][1,10]菲咯啉、aipm = 2-(9-蒽基)-1-甲基-咪唑并[4,5-][1,10]菲咯啉和pbtH = 2-苯基苯并噻唑，合成了两种基于蒽的配合物[Ir(pbt)(aip)]Cl ()和[Ir(pbt)(aipm)]Cl ()，以探究取代基R（在 中R = H，在 中R = CH）对光氧化活性和光氧化诱导发光的影响。1H NMR光谱和ES质谱表明，配合物 中的蒽部分在室温下用365 nm光照射时可被氧化。因此，该配合物表现出光氧化诱导的开启式黄色发光。与 相比，配合物 含有一个R = CH基团，导致光氧化活性非常弱。基于实验结果和量子化学计算，我们报道了 和 在光氧化行为以及相关发光调制方面的差异，并讨论了这些配合物中光氧化活性与取代基R之间的关系。
