A combined solvatochromic shift and TDDFT study probing solute-solvent interactions of blue fluorescent Alexa Fluor 350 dye: Evaluation of ground and excited state dipole moments.

Abstract

Herein we report, the effect of solvents on absorption and fluorescence spectra of Alexa Fluor-350 labelled fluorescent dye examined both experimentally and computationally. The steady state absorption and fluorescence measurements are carried out in a series of solvents to explore their solvatochromism and to determine its dipole moments. To this end, different empirical solvatochromic models like Bilot-Kawaski, Lippert-Mataga, Bakhshiev, Kawaski-Chamma-Viallet and Reichardt models are assessed against Alexa Fluor 350 dye to determine the singlet excited and ground state dipole moments. Computational studies were carried out to optimize ground and excited geometries using density functional theory (DFT) and time dependent density functional theory (TD-DFT), respectively, in vacuum. Additionally, this study encompasses estimation of the electronic transition energies from the ground to first excited state of dye employing TD-DFT. Further, TD-DFT has been combined with integral equation formalism of the polarizable continuum model (IEF-PCM) to calculate various solute-solvent interaction potentials which are then compared with experimental values. The highest occupied molecular orbital energy (HOMO), lowest unoccupied molecular orbital energy (LUMO), the energy gap, chemical hardness (η), softness (σ), electronegativity (χ) and chemical potential (μ) were estimated. Mulliken atomic charge, natural population analysis (NPA) and molecular electrostatic potential (MEP) map are correlated using density functional theory. The experimentally obtained ground and excited state dipole moments are compared with the ones obtained from computational and the results are discussed. NBO analysis is carried out to investigate the intramolecular charge transfer interactions and stabilization energy within the studied molecule.