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The influence of aggregation on the third-order nonlinear optical property of π-conjugated chromophores: the case of cyanine dyes.

The external molecular environment like the aggregation of molecules can significantly change the intrinsic third-order nonlinear optical (NLO) property of π-conjugated chromophores. A combined experimental and theoretical study was performed to understand the influence of the aggregation of cyanines on the third-order NLO property in spin-coated thin films. Our result indicates that the H and J type cyanine dimers prefer the polyene-like structures and the P type dimer displays a comparatively smaller bond length alternation (BLA). The polarizable continuum model (PCM)-tuned, range-separated (RSE) density functional approach was used to describe the screening effect of the cyanine aggregation. In the thin film, the P aggregate has very small positive isotropic averaged second hyperpolarizability γ, while the J aggregate has the largest positive γ due to the most polarized face-to-tail cyanine-cyanine interaction. Hence, the γ of the isolated cyanines (negative γ) may get cancelled against that of the cyanine aggregates (positive γ) in the thin film. The forward degenerate four-wave mixing technique also confirms a decrease in the magnitude of γ with an increase in the aggregation degree of cyanines. Since the large positive γ of the cyanine also implies strong two-photon absorption (TPA), the J aggregation of cyanines can be used as a potential fabrication method for applications involving TPA.