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Cooperative Interactions in Supramolecular Aggregates: Linear and Nonlinear Responses in Calix[4]arenes
Author(s) -
Datta Ayan,
Terenziani Francesca,
Painelli Anna
Publication year - 2006
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.200600336
Subject(s) - chromophore , polarizability , hyperpolarizability , intermolecular force , acceptor , chemistry , chemical physics , supramolecular chemistry , density functional theory , ground state , molecule , polar , nonlinear optics , computational chemistry , nonlinear system , photochemistry , organic chemistry , physics , atomic physics , quantum mechanics
The linear and nonlinear optical polarizabilities of donor–acceptor (D‐π‐A) chromophores in confined geometries of calix[4]arenes are investigated through a model for interacting polar‐polarizable molecules. Both the linear polarizability ( α ) and the first hyperpolarizability ( β ) decrease with increasing the interdipolar angle, as expected in the oriented‐gas picture. However, within the polar‐polarizable model we predict deviations from the additive result, irrespective of the interdipolar angle. Depending on the nature of the chromophore, electrostatic intermolecular interactions between polar and polarizable chromophores lead to cooperative damping or enhancement of the optical responses. Specifically, for chromophores whose ground state is dominated by the neutral D‐π‐A structure both α and β are suppressed with respect to the prediction of the oriented‐gas model, whereas the opposite holds true for chromophores whose ground state is dominated by the zwitterionic D + ‐π‐A − . These results explain recent experimental data on a calix[4]arene functionalized with a donor–acceptor dye for nonlinear optical applications. Density functional theory calculations on the relevant crystal structure further support our interpretation.