What is Solvatochromism?

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Abstract

Solvatochromism is commonly used in many fields of chemical and biological research to study bulk and local polarity in macrosystems (membranes, etc.), or even the conformation and binding of proteins. Despite its wide use, solvatochromism still remains a largely unknown phenomenon due to the extremely complex coupling of many different interactions and dynamical processes which characterize it. In this study we analyze the influence of different solvents on the photophysical properties of selected charge-transfer probes (4-AP, PRODAN, and FR0). The purpose is to achieve a microscopic understanding of the intermolecular effects which govern the absorption and fluorescence properties of solvated molecular probes, such as solvent-induced structural modifications, polarization effects, solubility, solute-solvent hydrogen-bonding interactions, and solute aggregation. To this aim we have exploited a time dependent density functional theory (TDDFT) approach coupled to complementary solvation approaches (continuum, discrete and mixed discrete and continuum). Such an integration has allowed us to clearly disentangle the complex interplay between specific and nonspecific interactions of the solvent with the probes and show that strong H-bonding effects not only can lead to large solvatochromic shifts but also can affect the nature of the emitting species with resulting reduction of the quantum yield.

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