Data di Pubblicazione:
2009
Citazione:
Enhancing the efficiency of two-photon absorption by metal coordination / L. Grisanti, C. Sissa, F. Terenziani, A. Painelli, D.M. Roberto, F. Tessore, R. Ugo, S. Quici, I. Fortunati, E. Garbin, C. Ferrante, R. Bozio. - In: PHYSICAL CHEMISTRY CHEMICAL PHYSICS. - ISSN 1463-9076. - 11:41(2009), pp. 9450-9457. [10.1039/b911268e]
Abstract:
The intensity of the two-photon absorption (TPA) spectrum of a terpyridine ligand acting as a
D–p–A chromophore (D = donor and A = acceptor) is enhanced by a factor of about 2 upon coordination to ZnCl2. Based on an analysis of linear absorption and fluorescence spectra of both the ligand and its Zn(II) complex, we have defined essential-state models for the two species. Linear and TPA spectra of the ligand are well reproduced in terms of a two-state model
accounting for the D–p–A 2D+–p–A charge resonance. However, the enhancement of the TPA response of its Zn(II) complex can only be understood by extending the model to account
for the active role of the ‘‘ZnCl2’’ moiety acting as a virtual Av acceptor group of a D–p–AAv structure. The virtual D+AAv state of the relevant three-state model has negligible weight in the ground state but contributes to the first excited state. The resulting increase of the excited-state dipole moment is responsible for the enhancement of the TPA cross section, and also explains the increase of the second order nonlinear optical response upon coordination.
Tipologia IRIS:
01 - Articolo su periodico
Elenco autori:
L. Grisanti, C. Sissa, F. Terenziani, A. Painelli, D.M. Roberto, F. Tessore, R. Ugo, S. Quici, I. Fortunati, E. Garbin, C. Ferrante, R. Bozio
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