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金属有机配合物 FeCp(CO) 对笼型硅锗簇 [Ge(Si(SiMe))] 在四氢呋喃溶液中动力学的影响:通过时间分辨吸收光谱法的合成与表征。

The influence of the FeCp(CO) moiety on the dynamics of the metalloid [Ge(Si(SiMe))] cluster in thf: synthesis and characterization by time-resolved absorption spectroscopy.

机构信息

Institut für Physikalische Chemie, Karlsruher Institut für Technologie (KIT), Kaiserstr. 12, 76131 Karlsruhe, Germany.

Institut für Anorganische Chemie, Universität Tübingen, Auf der Morgenstelle 18, 72076 Tübingen, Germany.

出版信息

Dalton Trans. 2019 Nov 7;48(41):15577-15582. doi: 10.1039/c9dt02091h. Epub 2019 Jul 26.

Abstract

A neutral tetrasubstituted Ge cluster with a covalently bound transition metal substituent was synthesized successfully via a salt metathesis reaction. Photoexcitation of [Ge(Si(SiMe))FeCp(CO)] induces excited state dynamics of the compound that was analysed by extended broadband fs absorption spectroscopy in the UV-Vis-NIR region. After UV or Vis excitation, an electron is detached from the [Ge(Si(SiMe))]-entity and localizes within few hundred fs. Recombination of this cluster-electron-pair occurs in about 7-9 ps. Finally, a third component can be attributed to complete ground state recovery within roughly 150 ps. This is much shorter compared to a longer-lived component within Li[Ge(Si(SiMe))], whose transient absorption exceeds the ns timescale after UV excitation. This observation emphasizes a strong influence of the Fe moiety.

摘要

通过盐交换反应成功合成了具有共价键合过渡金属取代基的中性四取代 Ge 簇。通过在 UV-Vis-NIR 区域进行扩展宽带 fs 吸收光谱分析,研究了[Ge(Si(SiMe))FeCp(CO)]的光激发诱导化合物的激发态动力学。在 UV 或 Vis 激发后,一个电子从[Ge(Si(SiMe))]-实体中脱离出来,并在几百 fs 内定位。这个簇-电子对的复合发生在大约 7-9 ps 内。最后,可以归因于大约 150 ps 内完全恢复基态的第三个组件。与 Li[Ge(Si(SiMe))]中寿命更长的组件相比,这要短得多,后者在 UV 激发后瞬态吸收超过 ns 时间尺度。这一观察结果强调了 Fe 部分的强烈影响。

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