The TDDFT Excitation Energies of the BODIPYs; The DFT and TDDFT Challenge Continues

Abstract

The derivatives of 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) are pivotal ingredients for a large number of functional, stimuli-responsive materials and therapeutic molecules based on their photophysical properties, and there is a urgent need to understand and predict their optical traits prior to investing a large amount of resources in preparing them. Density functional theory (DFT) and time-dependent DFT (TDDFT) computations were performed to calculate the excitation energies of the lowest-energy singlet excited state of a large series of common BODIPY derivatives employing various functional aiming at the best possible combination providing the least deviations from the experimental values. Using the common “fudge” correction, a series of combinations was investigated, and a methodology is proposed offering equal or better performances than what is reported in the literature.

Cyclopropyl Substituents Transform the Viscosity-Sensitive BODIPY Molecular Rotor into a Temperature Sensor

“…For computational efficiency, the −OC 10 H 21 group was truncated to a −OCH 3 group in all calculations. It is well known that TDDFT methods usually overestimate the absorption and emission energies of BODIPY fluorophores, , as is the case with our results. Nevertheless, the calculated spectra (Figure B) accurately reproduce the trend in maximum absorption and emission wavelengths seen in the experimental spectra.…”

Anti‐cooperative Self‐Assembly with Maintained Emission Regulated by Conformational and Steric Effects

“…ωB97X-D is a long-range corrected hybrid density functional with dispersion correction that is particularly suited for BODIPY derivatives. [47] Further computational details are given in the Supporting Information. In accordance with the literature, the calculations predict that the urea group of 1 prefers the trans-trans conformation.…”

Accurate predictions of the electronic excited states of BODIPY based dye sensitizers using spin-component-scaled double-hybrid functionals: a TD-DFT benchmark study

“…[46][47][48][49][50][51] Typically, push-pull dyes designed with the "electron donor-p linker-electron acceptor" (D-p-A) conventional architecture, and many other variations such as the D-A-p-A architecture, 52 are found to be efficient for photosensitized applications such as DSSCs. 14,53 Despite many theoretical and computational efforts, [54][55][56][57][58][59][60][61][62][63][64][65][66][67][68][69][70] the electronic molecular spectroscopy of BODIPYs is still not yet fully understood, and the accurate calculation of their excitedstates is still a challenge for both theoretical and computational chemists. In general, conventional time dependent (TD) DFT is the preferred method for electronic excited states calculations on large compounds, since it is efficient and reasonably accurate, with errors of transition energies in the range 0.1-0.3 eV for many simple organic chromophores.…”