Control of structure and photophysical properties by protonation and subsequent intramolecular hydrogen bonding

Protonation and subsequent intramolecular hydrogen bonding as methods to control chain structure and tune luminescence in heteroatomic conjugated polymers were reported experimentally [A. P. Monkman et al., J. Am. Chem. Soc. 124, 6049 (2002)]. In this paper, the structure and photophysical properties of the model teraryl compound of phenylene-pyridylene copolymer before and after protonation are theoretically studied with quantum chemistry methods. From the optimized ground states, intramolecular hydrogen bonding to the adjacent oxygen atom in the alkoxy substituent planarizes the backbone of the molecules, and the optimized detailed results of compound 9 before and after protonation, such as the dihedral angles between the central benzene and the two pyridyl rings, the bond lengths, and the bond angles, are consistent with the experimental results. From the results of the calculated excited states, the protonation and subsequent intramolecular hydrogen bonding result in the redshifts of the absorption, the increase of the ionization energy, the increase of the electron affinity, the decrease of the energy difference of the highest occupied molecular orbital and lowest unoccupied molecular orbital, the decrease of the binding gap, and the delocalization of the electron-hole coherence. The photophysical properties of compound 9 before and after protonation are further studied with a three-dimensional real-space analysis method of transition and charge difference densities (study transition dipole moment and charge transfer in the absorption and fluorescence processes) and two-dimensional real-space analysis method of transition density matrices (study the electron-hole coherence and the excitation delocalization). The calculated results show theoretically an insight understanding on the influence of the protonation and subsequent intramolecular hydrogen bonding to chain structure and photophysical properties.