Density Functional Theory Calculation on the Structural, Electronic, and Optical Properties of Fluorene-Based Azo Compounds

Abstract

In the present work, a theoretical study was carried out to study the molecular structure, harmonic vibrational frequencies, normal force field calculations, and Raman scattering activities for fluorene π-conjugation spacer containing azo-based dye named trans- and cis-bis(9H-fluoren-2-yl)diazene (AzoFL) at density functional theory using B3LYP (Becke-3-Lee-Yang-Parr) functional and 6-31+G(d,p) basis set. The theoretical calculations have also been performed with fluorene and the trans- and cis-isomers of diazene, difluorodiazene by the same method DFT-B3LYP/6-31+G(d,p) and basis set. The present DFT calculation shows that the trans-AzoFL is more stable than the cis-AzoFL by 16.33 kcal/mol. We also report the results of new assignments of vibrational frequencies obtained on the basis of the present calculations. Time-dependent DFT (TD-DFT) and ZIndo calculations have been performed to study the UV-vis absorption behavior and frontier molecular orbitals for the above-mentioned compounds. The UV-vis spectrum from TD-DFT calculation shows the π-π* transition bands at λ_max 423.53 nm (ε_max 6.0 × 10⁴ M^-1 cm^-1) and at λ_max 359.45 nm (ε_max 1.7 × 10⁴ M^-1 cm^-1), respectively, for trans- and cis-AzoFL. Compared to parent trans-diazene (λ_max 178.97 nm), a significant variation to longer wavelength (∼245 nm) is observed due to the incorporation of the fluorene (FL) ring into the -N=N- backbone. The co-planarity of the two FL rings with the longer N=N bond length compared to the unsubstituted parent diazene indicates the effective red shift due to the extended π-conjugation in trans-AzoFL. The nonplanarity of cis-AzoFL (48.1° tilted about the C-N bond relative to the planar N=N-C bond) reflects its ∼64 nm blue shift compared to that of trans-counterpart.