Dunlop David, Večeřa Miloš, Gyepes Róbert, Kubát Pavel, Lang Kamil, Horáček Michal, Pinkas Jiří, Šimková Ludmila, Liška Alan, Lamač Martin
J. Heyrovský Institute of Physical Chemistry of the Czech Academy of Sciences, Dolejškova 2155/3, 182 23 Praha 8, Czech Republic.
Department of Inorganic Chemistry, Faculty of Science, Charles University in Prague, Hlavova 2030, 128 40 Praha 2, Czech Republic.
Inorg Chem. 2021 May 17;60(10):7315-7328. doi: 10.1021/acs.inorgchem.1c00461. Epub 2021 May 4.
Cationic group 4 metallocene complexes with pendant imine and pyridine donor groups were prepared as stable crystalline [B(CF)] salts either by protonation of the intramolecularly bound ketimide moiety in neutral complexes [(η-CMe){η-CHCMeCMeC(R)═N-κ}MCl] (M = Ti, Zr, Hf; R = -Bu, Ph) by PhNMeH[B(CF)] to give [(η-CMe){η-CHCMeCMeC(R)═NH-κ}MCl][B(CF)] or by chloride ligand abstraction from the complexes [(η-CMe)(η-CHCMeCHCHN)MCl] (M = Ti, Zr) by Li[B(CF)]·2.5EtO to give [(η-CMe)(η-CHCMeCHCHN-κ)MCl][B(CF)]. Solid state structures of the new compounds were established by X-ray diffraction analysis, and their electrochemical behavior was studied by cyclic voltammetry. The cationic complexes of Zr and Hf, compared to the corresponding neutral species, exhibited significantly enhanced luminescence predominantly from triplet ligand-to-metal (LMCT) excited states with lifetimes up to 62 μs and quantum yields up to 58% in the solid state. DFT calculations were performed to explain the structural features and optical and electrochemical properties of the complexes.
通过以下两种方法制备了带有侧链亚胺和吡啶供体基团的阳离子第4族金属茂配合物，使其成为稳定的结晶[B(CF)]盐：一是用PhNMeH[B(CF)]使中性配合物[(η-CMe){η-CHCMeCMeC(R)═N-κ}MCl]（M = Ti、Zr、Hf；R = -Bu、Ph）中分子内键合的酮亚胺部分质子化，得到[(η-CMe){η-CHCMeCMeC(R)═NH-κ}MCl][B(CF)]；二是用Li[B(CF)]·2.5EtO从配合物[(η-CMe)(η-CHCMeCHCHN)MCl]（M = Ti、Zr）中夺取氯配体，得到[(η-CMe)(η-CHCMeCHCHN-κ)MCl][B(CF)]。通过X射线衍射分析确定了新化合物的固态结构，并通过循环伏安法研究了它们的电化学行为。与相应的中性物种相比，Zr和Hf的阳离子配合物在固态中表现出显著增强的发光，主要来自三重态配体到金属（LMCT）激发态，寿命长达62 μs，量子产率高达58%。进行DFT计算以解释配合物的结构特征以及光学和电化学性质。
