Merocyanines: Electronic Structure and Spectroscopy in Solutions, Solid State, and Gas Phase

Merocyanines, owing to their readily tunable electronic structure, are arguably the most versatile functional dyes, with ample opportunities for tailored design via variations of both the donor/acceptor (D/A) end groups and π-conjugated polymethine chain. A plethora of spectral properties, such as strong solvatochromism, high polarizability and hyperpolarizabilities, and sensitizing capacity, motivates extensive studies for their applications in light-converting materials for optoelectronics, nonlinear optics, optical storage, fluorescent probes, etc. Evidently, an understanding of the intrinsic structure–property relationships is a prerequisite for the successful design of functional dyes. For merocyanines, these regularities have been explored for over 70 years, but only in the past three decades have these studies expanded beyond the theory of their color and solvatochromism toward their electronic structure in the ground and excited states. This Review outlines the fundamental principles, essential for comprehension of the variable nature of merocyanines, with the main emphasis on understanding the impact of internal (chemical structure) and external (intermolecular interactions) factors on the electronic symmetry of the D−π–A chromophore. The research on the structure and properties of merocyanines in different media is reviewed in the context of interplay of the three virtual states: nonpolar polyene, ideal polymethine, and zwitterionic polyene.