Lone-Pair Delocalization Effects within Electron Donor Molecules: The Case of Triphenylamine and Its Thiophene-Analog

Triphenylamine (TPA) and its thiophene-analog, <i>N</i>,<i>N</i>-diphenyl-2-thiophenamine (DPTA), are both well-known as electron-donating molecules implemented in optoelectronic devices such as organic solar cells and LEDs. Comprehensive valence and core level photoelectron spectroscopy, as well as near edge X-ray absorption spectroscopy (NEXAFS), measurements have been performed on gas phase TPA and DPTA. The experimental results have been compared to density functional theory calculations, providing a detailed description of the molecular electronic structure. Specifically, the C 1s photoelectron lines of both TPA and DPTA were resolved in the different C atom contributions and their binding energies explained as the result of two counter-acting effects: (1) the electronegativity of the nitrogen atom (and sulfur atom in DPTA) and (2) the delocalization of the N (and S in DPTA) lone-pair electrons. In addition, the C K-edge NEXAFS spectrum of DPTA reveals that the lowest unoccupied molecular orbital (LUMO) energy position is affected differently if the core–hole site is on the phenyl compared to the thiophene ring. The electron-donating properties of these two molecules are largely explained by the significant contribution of the N lone-pair electrons (p_<i>z</i>) to the highest occupied molecular orbital. The contribution to the LUMO and to the empty density of states of the sulfur of the thiophene ring in DPTA explains the better performance of donor−π–acceptor molecules containing this moiety and implemented in photoenergy conversion devices