Anti-Kasha’s Rule Fluorescence Emission in (2-Ferrocenyl)indene Generated by a Twisted Intramolecular Charge-Transfer (TICT) Process

A twisted intramolecular charge-transfer (TICT) process has been identified in (2-ferrocenyl)indene. This photochemical process explains the anti-Kasha’s rule fluorescence emission observed for this system. Experimental and model investigations on (2-ferrocenyl)tetramethylindene and (2-ferrocenyl)-h...

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Published inThe journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 115; no. 30; pp. 8344 - 8349
Main Authors Scuppa, Stefano, Orian, Laura, Donoli, Alessandro, Santi, Saverio, Meneghetti, Moreno
Format Journal Article
LanguageEnglish
Published United States American Chemical Society 04.08.2011
Subjects
A: Dynamics, Clusters, Excited States
Charge transfer
Emission spectroscopy
Fluorescence
Indene
Indenes - chemistry
Mathematical analysis
Molecular Structure
Photochemical
Photochemical Processes
Physical chemistry
Quantum Theory
Spectroscopy
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Summary:A twisted intramolecular charge-transfer (TICT) process has been identified in (2-ferrocenyl)indene. This photochemical process explains the anti-Kasha’s rule fluorescence emission observed for this system. Experimental and model investigations on (2-ferrocenyl)tetramethylindene and (2-ferrocenyl)-hexamethylindene were also performed, in order to evaluate the effect of a steric hindrance on the TICT mechanism. The energy of the lowest main excited states was computed with a TD-DFT approach, as a function of the rotation of the dihedral angle between the indene and the cyclopentadienyl planes. To the best of our knowledge, this is the first example of TICT generated by metal-to-ligand charge transfer (MLCT) in a ferrocene-containing complex and, more generally, the first case of complexes in which a metal center is directly involved.
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ISSN:1089-5639
1520-5215
DOI:10.1021/jp2021227