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

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• 作者：Stefano Scuppa ; Laura Orian ; Alessandro Donoli ; Saverio Santi ; Moreno Meneghetti
• 刊名：Journal of Physical Chemistry A
• 出版年：2011
• 出版时间：August 4, 2011
• 年：2011
• 卷：115
• 期：30
• 页码：8344-8349
• 全文大小：836K
• 年卷期：v.115,no.30(August 4, 2011)
• ISSN：1520-5215

文摘

A twisted intramolecular charge-transfer (TICT) process has been identified in (2-ferrocenyl)indene. This photochemical process explains the anti-Kasha鈥檚 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.