A molecular descriptor of intramolecular noncovalent interaction for regulating optoelectronic properties of organic semiconductors

In recent years, intramolecular noncovalent interaction has become an important means to modulate the optoelectronic performances of organic/polymeric semiconductors. However, it lacks a deep understanding and a direct quantitative relationship among the molecular geometric structure, strength of noncovalent interaction, and optoelectronic properties in organic/polymeric semiconductors. Herein, upon systematical theoretical calculations on 56 molecules with and without noncovalent interactions (X···Y, X = O, S, Se, Te; Y = C, F, O, S, Cl), we reveal the essence of the interactions and the dependence of its strength on the molecular geometry. Importantly, a descriptor S is established as a function of several basic geometric parameters to well characterize the noncovalent interaction energy, which exhibits a good inverse correlation with the reorganization energies of the photo-excited states or electron-pumped charged states in organic/polymeric semiconductors. In particular, the experimental (1)H, (77)Se, and (125)Te NMR, the optical absorption and emission spectra, and single crystal structures of eight compounds fully confirm the theoretical predictions. This work provides a simple descriptor to characterize the strength of noncovalent intramolecular interactions, which is significant for molecular design and property prediction.