Study on the modulation of spectral properties of the formylperylene–methanol clusters by excited-state hydrogen bonding strengthening

Abstract

In the present work, the charge transfer (CT) process within the formylperylene (FPe)–methanol (MeOH) systems facilitated by intermolecular hydrogen bonding interactions is theoretically studied in both the ground state S0 and the first singlet excited state S1. The geometric structures, electronic spectra and the infrared spectra of the FPe monomer as well as the various hydrogen-bonded FPe–MeOH complexes in both states were calculated with the density functional theory (DFT) method and time-dependent density functional theory (TD-DFT) methods, respectively. It is demonstrated that the total effect of the intermolecular hydrogen bonding between FPe and the MeOH molecules becomes strengthened in the ground state as the number of the MeOH molecules hydrogen-bonded to the FPe molecule increases from zero to three, which induces large increases in the dipole moment as well as systemic redshifts of the absorption spectra of FPe. Furthermore, upon photoexcitation of the FPe molecule, the intermolecular hydrogen bonds formed in the various hydrogen-bonded FPe–MeOH complexes are further strengthened which leads to even larger dipole moments as well as obvious redshifts of the fluorescence spectra. The calculated electronic spectra of the various hydrogen-bonded FPe–MeOH complexes are in agreement with the steady-state absorption and fluorescence spectra of FPe observed in the binary mixed solvents with different MeOH concentration. The intermolecular hydrogen bonding strengthening in both the ground and excited states are further confirmed by the infrared spectra shifts. Moreover, the vitally important role played by the intermolecular hydrogen bonding interaction and its strengthening upon electronic excitation in the CT process is discussed.