Charge Transfer through Isomeric Unsaturated Hydrocarbons. Redox Switchable Optical Properties and Electronic Structure of Substituted Indenes with a Pendant Ferrocenyl
详细信息 查看全文
- 作者：Saverio Santi ; Laura Orian ; Alessandro Donoli ; Christian Durante ; Annalisa Bisello ; Paolo Ganis ; Alberto Ceccon ; Laura Crociani ; Franco Benetollo
- 刊名：Organometallics
- 出版年：2007
- 出版时间：November 19, 2007
- 年：2007
- 卷：26
- 期：24
- 页码：5867 - 5879
- 全文大小：545K
- 年卷期：v.26,no.24(November 19, 2007)
- ISSN：1520-6041
文摘
A family of (ferrocenyl)indenes, (2-ferrocenyl)indene, (2-ferrocenyl)tetramethylindene, (2-ferrocenyl)hexamethylindene, (3-ferrocenyl)indene, and (3-ferrocenyl)hexamethylindene, and the correspondingmonooxidized cations have been prepared. The results of a structural and spectroelectrochemical studyare discussed. The availability of pairs of isomers with known geometries and differently methylatedindenes allowed the detailed investigation of how slight geometric and electronic modifications affecttheir physical properties. The molecular structures have been determined by X-ray diffraction and comparedwith the fully optimized structures calculated with state-of-the-art DFT methods. Calculated andcrystallographic structures agree in establishing the dependence of the orientation of the indene moietyand the ferrocenyl cyclopentadienyl rings on the degree of methylation. The UV-vis spectra and inparticular the appearance upon oxidation of a new near-IR absorption, whose energy and intensity increasewith the degree of methylation and cyclopentadienyl-indene planarity, are rationalized in the frameworkof the Hush theory and at quantum chemistry level by DFT and TD-DFT calculations.