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Issue 12, 2006
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Dipolar interactions and hydrogen bonding in supramolecular aggregates: understanding cooperative phenomena for 1st hyperpolarizability

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Abstract

Weak intermolecular forces like dipolar interactions and hydrogen-bonding lead to a variety of different packing arrangements of molecules in crystals and self-assemblies. Such differences in the arrangements change the extent of excitonic splitting and excitation spectra in the multichromophore aggregates. In this tutorial review, the role of such interactions in fine tuning the linear and 1st non-linear optical (NLO) responses in molecular aggregates are discussed. The non-additivity of these optical properties arise specifically due to such cooperative interactions. Calculations performed on dimers, trimers and higher aggregates for model systems provide insights into the interaction mechanisms and strategies to enhance the 1st hyperpolarizabilities of π-conjugated molecular assemblies. Flexible dipole orientations in the alkane bridged chromophores show odd-even variations in their second-harmonic responses that are explained through their dipolar interactions in different conformations. Parameters for the optical applications of molecules arranged in constrained geometry, like in Calix[n]arene, have been elucidated. We also highlight the recent developments in this field of research together with their future prospects.

Graphical abstract: Dipolar interactions and hydrogen bonding in supramolecular aggregates: understanding cooperative phenomena for 1st hyperpolarizability

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Article information


Submitted
07 Aug 2006
First published
13 Oct 2006

Chem. Soc. Rev., 2006,35, 1305-1323
Article type
Critical Review

Dipolar interactions and hydrogen bonding in supramolecular aggregates: understanding cooperative phenomena for 1st hyperpolarizability

A. Datta and S. K. Pati, Chem. Soc. Rev., 2006, 35, 1305
DOI: 10.1039/B605478A

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