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Photoinduced Charge-Transfer Reactions of Tricyanoethlene with Aromatic Hydrocarbon Electron Donors. I. Emission Studies of Naphthalene-Tricyanoethylene Exciplex

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Dresner J., Kwapisz K., Deperasińska I., Prochorow J., Bruni P., Giardina A., Tosi G.

Acta Physica Polonica A

2002

vol. 102

issue 3

443-468

The fluorescence quenching of a series of aromatic hydrocarbon electron donors by an electron acceptor tricyanoethylene has been observed. The quenching mechanism is consistent with the charge-transfer (or electron-transfer) mechanism, as indicated by the appearance of a new, broad, and structureless exciplex emission band. Detailed, steady-state, and time-resolved emission studies of the kinetics and thermodynamics of exciplex formation and relaxation have been performed for naphthalene-tricyanoethylene system. It was found that the kinetics of monomer-exciplex equilibrium for this system, in a non-polar solvent (n-hexane), can be described in terms of a simple two-state photokinetic scheme. Within such a scheme, under conditions of the present experiment, napthalene-tricyanoethylene system approaches the limits under which exciplex formation is very effective - it becomes exclusively diffusion-controlled and at the same time a competitive process of thermal dissociation of exciplex ceases to operate. This leads to a very rarely observed reversal of physical meaning of the decay parameters which are describing the rise and the decay of exciplex fluorescence.

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1 Acta Physica Polonica A

1 2002

1 Bruni P.

1 Deperasińska I.

1 Dresner J.

1 Giardina A.

1 Kwapisz K.

1 Prochorow J.

1 Tosi G.

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Photoinduced Charge-Transfer Reactions of Tricyanoethlene with Aromatic Hydrocarbon Electron Donors. I. Emission Studies of Naphthalene-Tricyanoethylene Exciplex