Study of hydrogen-bonding, vibrational dynamics and structure-activity relationship of genistein using spectroscopic techniques coupled with DFT

Abstract The conformational and hydrogen bonding studies of genistein have been performed by combined spectroscopic and quantum chemical approach. The vibrational spectra (FT-IR and FT-Raman), UV–visible and 1 H and 13 C NMR absorption spectra of genistein have been recorded and examined. The vibrational wavenumbers of optimized geometry and total energy for isolated molecule and hydrogen-bonded dimers of genistein have been determined using the quantum chemical calculation (DFT/B3LYP) with extended 6–311++G (d,p) basis set. The vibrational assignments for the observed FT-IR and FT-Raman spectra of genistein are provided by calculations on monomer and hydrogen-bonded dimer. The quantum theory of atoms in molecules (QTAIM) is used for investigating the nature and strength of hydrogen-bonds. UV–visible spectrum of the genistein was recorded in methanol solvent and the electronic properties were calculated by using time-dependent density functional theory (TD–DFT). The computed HOMO and LUMO energies predicted the type of transition as π → π*. The 1 H and 13 C NMR signals of the genistein were computed by the Gauge including atomic orbital (GIAO) approach. Natural bond orbital (NBO) analysis predicted the stability of molecules due to charge delocalization and hyper conjugative interactions. NBO analysis shows that there is an O H⋯O inter and intramolecular hydrogen bond, and π → π* transition in the monomer and dimer, which is consistent with the conclusion obtained by the investigation of molecular structure and assignment of UV–visible spectra.