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Issue 9, 2011
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Competitive photocyclization/rearrangement of 4-aryl-1,1-dicyanobutenes controlled by intramolecular charge-transfer interaction. Effect of medium polarity, temperature, pressure, excitation wavelength, and confinement

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Abstract

A series of 4-aryl-1,1-dicyanobutenes (1a–1f) with different substituents were synthesized to control the intramolecular donor–acceptor or charge-transfer (C–T) interactions in the ground state. Photoexcitation of these C–T substrates led to competitive cyclization and rearrangement, the ratio being critically controlled by various environmental factors, such as solvent polarity, temperature and static pressure, and also by excitation wavelength and supramolecular confinement (polyethylene voids). In non-polar solvents, the rearrangement was dominant (>10 : 1) for all examined substrates, while the cyclization was favoured in polar solvents, in particular at low temperatures. Selective excitation at the C–T band further enhanced the cyclization up to >50 : 1 ratios. More importantly, the cyclization/rearrangement ratio was revealed to be a linear function of the C–T transition energy. However, the substrates with a sterically demanding or highly electron-donating substituent failed to give the cyclization product.

Graphical abstract: Competitive photocyclization/rearrangement of 4-aryl-1,1-dicyanobutenes controlled by intramolecular charge-transfer interaction. Effect of medium polarity, temperature, pressure, excitation wavelength, and confinement

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Publication details

The article was received on 27 Jan 2011, accepted on 15 Feb 2011 and first published on 04 Mar 2011


Article type: Paper
DOI: 10.1039/C1PP05038A
Citation: Photochem. Photobiol. Sci., 2011,10, 1405-1414
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    Competitive photocyclization/rearrangement of 4-aryl-1,1-dicyanobutenes controlled by intramolecular charge-transfer interaction. Effect of medium polarity, temperature, pressure, excitation wavelength, and confinement

    T. Ito, E. Nishiuchi, G. Fukuhara, Y. Inoue and T. Mori, Photochem. Photobiol. Sci., 2011, 10, 1405
    DOI: 10.1039/C1PP05038A

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