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Effects of Substituents on the Length of Central C(sp^3)-C(sp^3) Bond in Anthracene Photodimers and Related Molecules

Dougherty, Dennis A. and Choi, Chang Sun and Kaupp, Gerd and Buda, Andrzej B. and Rudziński, Jerzy M. and Ōsawa, Eiji (1986) Effects of Substituents on the Length of Central C(sp^3)-C(sp^3) Bond in Anthracene Photodimers and Related Molecules. Journal of the Chemical Society-Perkin Transactions 2 (7). pp. 1063-1070. ISSN 1472-779X. doi:10.1039/P29860001063.

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Effects of substituents on the lengths of the central C–C single bond in the butterfly-shaped anthracene photodimers (1)–(7) and lepidopterenes (8) are studied. X-Ray analysis of the photodimer (10) of 9,10-difluoroanthracene gave a C(9)–C(10′) bond length of 1.631 (3)Å. An attempt to re-determine molecular structure of the photoisomer (5) of [2.2](9,10) anthracenophane (12) by neutron diffraction analysis is also reported [C(9)–C(10′): obs. 1.64(1), calc. 1.63(1)Å]. The D_2 structure that had been proposed for the minimum-energy conformation of (5) is questioned and the D_(2h) symmetric conformation is suggested on the basis of the diffraction results and MNDO calculations. The experimentally determined distances of the long central C–C bonds in these butterfly compounds including dianthronyl (9) are well reproduced by MNDO calculations with a standard deviation of 0.013 Å. Small but significant further elongation of the central C–C bond by up to 0.07 Å resulting from annulation of cyclobutane or cyclopentane ring in anthracene photodimers and from remote chlorine substitution in lepidopterene are interpreted in terms of the increased π→σ^* orbital interaction.

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Dougherty, Dennis A.0000-0003-1464-2461
Additional Information:© 1986 Royal Society of Chemistry. Received 10th June 1985; Paper 5/978. This work was supported by a Grant-in-Aid for Scientific Research from the Ministry of Education at Sapporo and by a Camille and Henry Dreyfus Grant for Newly Appointed Young Faculty in Chemistry at Pasadena. G. K. thanks Dr. W. Littke for technical advice and for making available his microscope facilities. D. A. D. thanks Professor R. E. Marsh for helpful discussions and J. A. Rice, Caltech, for technical assistance. Calculations have been carried out at the Computing Centers of Hokkaido University and the Institute of Molecular Science, and at Caltech on the Theoretical Chemistry Computer funded through grants from the Camille and Henry Dreyfus Foundation, the National Science Foundation, and the Sloan Fund of the California Institute of Technology.
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Ministry of Education (Japan)UNSPECIFIED
Camile and Henry Dreyfus FoundationUNSPECIFIED
Alfred P. Sloan FoundationUNSPECIFIED
Issue or Number:7
Record Number:CaltechAUTHORS:20120627-071330188
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Official Citation:Effects of substituents on the length of central C(sp3)–C(sp3) bond in anthracene photodimers and related molecules Dennis A. Dougherty, Chang Sun Choi, Gerd Kaupp, Andrzej B. Buda, Jerzy M. Rudziński and Eiji Ōsawa J. Chem. Soc., Perkin Trans. 2, 1986, 1063-1070 DOI: 10.1039/P29860001063
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:32115
Deposited By: Ruth Sustaita
Deposited On:27 Jun 2012 14:55
Last Modified:09 Nov 2021 21:15

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