Singlet Fission in a Pyrrole-Fused Cross-Conjugated Skeleton with Adaptive Aromaticity
Long Wang, Lu Lin, Jingjing Yang, Yishi Wu, Hua Wang, Jun Zhu, Jiannian Yao, Hongbing Fu
Abstract
Singlet fission (SF) materials hold the potential to increase the power conversion efficiency of solar cells by reducing the thermalization of high-energy excited states. The major hurdle in realizing this potential is the limited scope of SF-active materials with high fission efficiency, suitable energy levels, and sufficient chemical stability. Herein, using theoretical calculation and time-resolved spectroscopy, we developed a highly stable SF material based on dipyrrolonaphthyridinedione (DPND), a pyrrole-fused cross-conjugated skeleton with a distinctive adaptive aromaticity (dual aromaticity) character. The embedded pyrrole ring with 4n+2 π-electron features aromaticity in the ground state, while the dipole resonance of the amide bonds promotes a 4n π-electron Baird’s aromaticity in the triplet state. Such an adaptive aromaticity renders the molecule efficient for the SF process [E(S1) ≥ 2E(T1)] without compromising its stability. Up to 173% triplet yield, strong blue-green light absorption, and suitable triplet energy of 1.2 eV, as well as excellent stability, make DPND a promising SF sensitizer toward practical applications.