Combined molecular and supramolecular bottom-up engineering for enhanced nonlinear optical response

We present the results of the combination of two independently valid optimization strategies for the first hyperpolarizability of ionic organic chromophores. The first strategy to enhance the nonlinear optical response, at the molecular level, is the extension of the conjugation path in the chromophore itself. The second strategy, at the supramolecular level, is the bottom-up nano-engineering of an inclusion complex of the chromophore in an amylose helix by self-assembly. We have studied a series of five (dimethylamino)stilbazolium-type chromophores with increasing conjugation length between the (dimethylamino)phenyl donor ring and the pyridinium acceptor ring in combination with four amylose helices of different molecular weights. The first hyperpolarizability of the self-assembled inclusion complexes has been experimentally determined by frequency-resolved femtosecond hyper-Rayleigh scattering at 800 and 1300 nm. These values are compared with experimental values for the free chromophores in solution and with theoretical values. Where experimental values for the hyperpolarizability in solution were lower than theoretically predicted, an enhancement upon inclusion was observed - with the longest chromophore in the best amylose helix showing an enhancement by one order of magnitude. Molecular modelling of the inclusion of the chromophore suggests that the coplanarity of the two rings is more important than all-trans configuration in the conjugation path. The degree of enhancement, however, is not enough to breach the apparent limit of the first hyperpolarizability which is about an order of magnitude below the fundamental limit calculated by Kuzyk. This analysis confirms the determining role of the arrangement of the excited-state energy levels on the nonlinear response.

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