C. Eugene Bennett Department of Chemistry, West Virginia University, 100 Prospect Street, Morgantown, WV, 26506, USA.
Chemistry. 2019 Feb 26;25(12):3042-3052. doi: 10.1002/chem.201804671. Epub 2019 Feb 7.
Luminescent seven-coordinated zirconium and hafnium complexes bearing three mono-anionic 2,2'-pyridylpyrrolide ligands and one chloride were synthesized. Solid-state structures and the dynamic behaviors in solution were probed by X-ray crystallography and variable temperature H NMR experiments, respectively. Absorption spectroscopy and time-dependent density functional theory (TD-DFT) calculations supported a hybrid of ligand-to-metal charge transfer (LMCT)/ligand-to-ligand charge transfer (LLCT) for the visible light absorption band. The complexes ( PMP ) MCl (M=Zr, Hf, PMP =3,5-dimethyl-2-(2-pyridyl)pyrrolide) are emissive in solution at room temperature upon irradiation with visible light due to a combination of phosphorescence and fluorescence characterized by excited state lifetimes in the μs and low to sub-ns timescale, respectively. Electrochemical experiments revealed that the zirconium complex possesses a reversible redox event under highly reducing condition (-2.29 V vs. Fc ).
合成了具有三个单阴离子 2,2'-联吡啶吡咯烷配体和一个氯离子的发光七配位锆和铪配合物。通过 X 射线晶体学和变温 H NMR 实验分别研究了其在固态结构和溶液中的动态行为。吸收光谱和含时密度泛函理论（TD-DFT）计算支持可见光吸收带的配体到金属电荷转移（LMCT）/配体到配体电荷转移（LLCT）混合。由于磷光和荧光的组合，（PMP）MCl（M=Zr，Hf，PMP=3,5-二甲基-2-(2-吡啶基)吡咯烷）在可见光照射下在室温下在溶液中具有发光性，其特征分别为在 μs 和低至亚 ns 时间尺度的激发态寿命。电化学实验表明，在高度还原条件（-2.29 V 相对于 Fc）下，锆配合物具有可逆的氧化还原事件。
