Connecting the dots for fundamental understanding of structure–photophysics–property relationships of COFs, MOFs, and perovskites using a Multiparticle Holstein Formalism

Photoactive organic and hybrid organic–inorganic materials such as conjugated polymers, covalent organic frameworks (COFs), metal–organic frameworks (MOFs), and layered perovskites, display intriguing photophysical signatures upon interaction with light. Elucidating structure–photophysics–property relationships across a broad range of functional materials is nontrivial and requires our fundamental understanding of the intricate interplay among excitons (electron–hole pair), polarons (charges), bipolarons, phonons (vibrations), inter-layer stacking interactions, and different forms of structural and conformational defects. In parallel with electronic structure modeling and data-driven science that are actively pursued to successfully accelerate materials discovery, an accurate, computationally inexpensive, and physically-motivated theoretical model, which consistently makes quantitative connections with conceptually complicated experimental observations, is equally important. Within this context, the first part of this perspective highlights a unified theoretical framework in which the electronic coupling as well as the local coupling between the electronic and nuclear degrees of freedom can be efficiently described for a broad range of quasiparticles with similarly structured Holstein-style vibronic Hamiltonians. The second part of this perspective discusses excitonic and polaronic photophysical signatures in polymers, COFs, MOFs, and perovskites, and attempts to bridge the gap between different research fields using a common theoretical construct – the Multiparticle Holstein Formalism. We envision that the synergistic integration of state-of-the-art computational approaches with the Multiparticle Holstein Formalism will help identify and establish new, transformative design strategies that will guide the synthesis and characterization of next-generation energy materials optimized for a broad range of optoelectronic, spintronic, and photonic applications.