Photoexcitation of Ge9- Clusters in THF: New Insights into the Ultrafast Relaxation Dynamics and the Influence of the Cation.

Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry
Nadine C MichenfelderAndreas-Neil Unterreiner

Abstract

We present a comprehensive femtosecond (fs) transient absorption study of the [Ge9(Hyp)3]- (Hyp = Si(SiMe3)3) cluster solvated in tetrahydrofuran (THF) with special emphasis on intra- and intermolecular charge transfer mechanisms which can be tuned by exchange of the counterion and by dimerization of the cluster. The examination of the visible and the near infrared (NIR) spectral range reveals four different processes of cluster dynamics after UV (267/258 nm) photoexcitation related to charge transfer to solvent and localized excited states in the cluster. The resulting transient absorption is mainly observed in the NIR region. In the UV-Vis range transient absorption of the (neutral) cluster core with similar dynamics can be observed. By transferring concepts of: (i) charge transfer to the solvent known from solvated Na- in THF and (ii) charge transfer in bulk-like materials on metalloid cluster systems containing [Ge9(Hyp)3]- moieties, we can nicely interpret the experimental findings for the different compounds. The first process occurs on a fs timescale and is attributed to localization of the excited electron in the quasi-conduction band/excited state which competes with a charge transfer to the solvent. The latter leads t...Continue Reading

References

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Jul 28, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Nadine C MichenfelderAndreas-Neil Unterreiner

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Citations

May 13, 2021·Chemical Communications : Chem Comm·Svetlana V KlementyevaAndreas Schnepf

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Methods Mentioned

BETA
X-Ray
NMR

Software Mentioned

MATLAB

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