Photoinduced Electron Transfer Processes in Rotaxanes Containing [60]Fullerene and Ferrocene: Effect of Axle Charge on Light-Induced Molecular Motion
Atula S. D. Sandanayaka A , Hisahiro Sasabe B , Yasuyuki Araki A , Nobuhiro Kihara B , Yoshio Furusho C , Toshikazu Takata D E and Osamu Ito A EA Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Sendai 980-8577 Japan.
B Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, Osaka 599-8531, Japan.
C Yashima Super-Structured Helix Project, Japan Science and Technology Agency, Nagoya 552-8555, Japan.
D Department of Organic and Polymeric Materials, Tokyo Institute of Technology, Tokyo 152-8552, Japan.
E Corresponding authors. Email: ttakata@polymer.titech.ac.jp; ito@tagen.tohoku.ac.jp
Australian Journal of Chemistry 59(3) 186-192 https://doi.org/10.1071/CH05311
Submitted: 16 November 2005 Accepted: 18 January 2006 Published: 24 March 2006
Abstract
Two rotaxanes containing [60]fullerene (C60) as pendants on a crown-ether necklace, to which ferrocene (Fc) as axle stoppers were added, have been synthesized. One rotaxane has an ammonium cation in the centre of the axle (C60;Fc)Rot+ and the other has a neutral axle (C60;Fc)Rot. Optimized structures, calculated using a molecular orbital method, suggest that in the ground states (C60;Fc)Rot+ has a shorter distance between C60 and Fc than that of (C60;Fc)Rot. In both rotaxanes, efficient intra-rotaxane photoinduced electron-transfer processes have been observed by the selective excitation of C60 which acts as a photosensitized electron acceptor. The rates and efficiencies of the charge-separation and charge-recombination processes were evaluated by time-resolved fluorescence and transient absorption measurements with changing solvent polarity. From the different kinetic parameters between (C60;Fc)Rot+ and (C60;Fc)Rot, the light-induced molecular motions of these rotaxanes in the excited states and charge-separated states were separately revealed.
Acknowledgments
This present work was supported by a Grants-in-Aid on Scientific Research on Priority Areas (417) from the Ministry of Education, Culture, Sports, Science and Technology of Japan.
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