Manipulating Excited State Properties of Iridium Phenylpyridine Complexes with “Push–Pull” Substituents
Manipulating Excited State Properties of Iridium Phenylpyridine Complexes with “Push–Pull” Substituents
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操纵具有“推拉”取代基的铱苯基吡啶配合物的激发态性质
DOI：
10.1021/acs.inorgchem.2c02269
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发表时间：
2022
影响因子：
4.6
通讯作者：
Rack, Jeffrey J.
中科院分区：
文献类型：
--
作者：
Turner, Emigdio E.;Breen, Douglas J.;Kosgei, Gilbert;Crandall, Laura A.;Curtin, Gregory M.;Jakubikova, Elena;O’Donnell, Ryan M.;Ziegler, Christopher J.;Rack, Jeffrey J.
我们合成了一系列[IrIII（ppy）2（L）]n+型配合物（1-4），其中ppy是取代的2-苯基吡啶，L是螯合膦硫醚配体。母体配合物（1）含有一个未取代的苯基吡啶配体，而配合物（2）的吡啶环上含有一个硝基取代基，配合物（3）的苯环上含有一个二苯胺基，配合物（4）同时含有硝基和二苯胺基。晶体学、1H NMR和元素分析数据与每个化学式一致。DFT（密度泛函理论）计算结果显示了Ir、ppy和PS配体的复杂电子结构。超快泵浦-探测数据显示了苯基吡啶部分的强贡献以及强全色激发态吸收跃迁。数据表明，硝基和/或二苯胺取代基占主导地位的光谱这一系列的化合物。
We have prepared a series of complexes of the type [IrIII(ppy)2(L]n+complexes (1–4), where ppy is a substituted 2-phenylpyridine and L is a chelating phosphine thioether ligand. The parent complex (1) comprises an unsubstituted phenylpyridine ligand, whereas complex2contains a nitro substituent on the pyridine ring, complex3features a diphenylamine group on the phenyl ring, and4has both nitro and diphenylamine groups. Crystallographic,1H NMR, and elemental analysis data are consistent with each of the chemical formulae. DFT (density functional theory) computational results show a complicated electronic structure with contributions from Ir, ppy, and the PS ligand. Ultrafast pump–probe data show strong contributions from the phenylpyridine moieties as well as strong panchromatic excited state absorption transitions. The data show that nitro and/or diphenylamine substituents dominate the spectroscopy of this series of compounds.