Triangulenium dyes: the comprehensive photo-absorption and emission story of a versatile family of chromophores

The triangulenium dyes constitute a family of versatile chromophores whose impressive photo-absorption and emission properties are currently highlighted in numerous novel experimental applications. In this investigation, we provide a comprehensive TDDFT characterization of their spectroscopic properties elucidating the origin of their large and complex absorption and emission vibronic spectra spread over the (whole) visible region. More precisely, by benchmarking the performance of 10 commonly-used exchange-correlation density functionals belonging to different classes of approximation, we develop and validate a computational protocol allowing the accurate modeling of both the position and optical line-shape of their vibrationally-resolved absorption and emission band structures. We find that semilocal approximations provide the best estimate of the structure of the vibronic spectra, however they spuriously and strongly underestimate their position. We finally show that global-hybrid density functionals mixing between 20 and 30% of exact-like exchange are an excellent compromise to get a satisfactory estimate of both of these properties.