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Global and Target Analysis of Time-Resolved Fluorescence Spectra of Di-9H-fluoren-9-yldimethylsilane: Dynamics and Energetics for Intramolecular Excimer Formation

Global and Target Analysis of Time-Resolved Fluorescence Spectra of Di-9H-fluoren-9-yldimethylsilane: Dynamics and Energetics for Intramolecular Excimer Formation

Bong Hyun Boo, Dongeun Kang

J Phys Chem A. 2005 May 19;109(19):4280-4.

PMID: 16833757

Abstract:

Dynamics and energetics for intramolecular excimer formation of a diarylsilane, di-9H-fluoren-9-yldimethylsilane (DFYDMS) have been investigated by means of ps time-resolved fluorescence spectroscopy and ab initio calculation. Multiple fluorescence decay curves were globally deconvolved to generate time-resolved fluorescence spectra and decay-associated spectra (DAS), from which species-associated spectra (SAS) were obtained. It is shown in the global analysis that there are at least three excited states: Two states are the locally excited (LE) states (lambda(max) approximately 320 nm) having lifetimes of 0.70 +/- 0.04 and 1.75 +/- 0.02 ns, and another is the excimer state (lambda(max) approximately 400 nm) having a lifetime of 7.34 +/- 0.02 ns. The species which decays with 0.70 ns evolves into a species with a red-shifted spectrum, which in turn decays in 7.34 ns. The experimental and ab initio results indicate that the rise time of 0.70 ns corresponds to the conversion of the initial S(1) LE state having a near sandwich geometry to the S(1) excimer state adopting a true sandwich geometry.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP18769001	Di-9H-fluoren-9-yldimethylsilane		18769-00-1	Price

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