Structural and Electronic (Absorption and Fluorescence) Properties of a Stable Triplet Diphenylcarbene: A DFT Study

A triplet diphenylcarbene, bis[3-bromo-5-(trifluoromethyl)[1,1'-biphenyl]-4-yl]methylidene (B3B), with exceptional stability was discovered by chemists from Japan's Mie University. To investigate its different quantum chemical features, a theoretical analysis was predicated on Density Functional Theory (DFT) and Time Dependent-DFT (TD-DFT) based technique. According to the findings, the singlet-triplet energy gap (ES-T), as well as HOMO-LUMO energy bandgap (E_H-L), was found to be diminished when nucleophilicity (N) rose. We looked at the geometrical dimensions, molecular orbitals (MOs), electronic spectra, electrostatic potential, molecular surfaces, reactivity characteristics, and thermodynamics features of the title carbene (B3B). Its electronic spectra in different solvents were calculated using TD-DFT and Polarizable Continuum Model (PCM) framework. The estimated absorption maxima of B3B were seen between 327 and 340 nm, relying on the solvents, and were attributed to the S⁰ → S¹ transition. Estimated fluorescence spectral peaks were found around 389 and 407 nm with the S¹ and S⁰ transitions being identified. Its fluorescence/absorption intensities revealed a blue shift change when the solvent polarity was increased. The least exciting state has been discovered to be the π → π^* charge-transfer (CT) phase. According to the Natural Bonding Orbital (NBO) exploration, ICT offers a significant role in chemical system destabilization. Furthermore, several hybrid features were used to determine the NLO (nonlinear optical) features (polarizability, first-order hyperpolarizability, and dipole moment). The calculated values suggest that B3B is a promising candidate for further research into nonlinear optical properties.