Beyond Conformational Control: Effects of Noncovalent Interactions on Molecular Electronic Properties of Conjugated Polymers

[Image: see text] Tuning the electronic properties of polymers is of great importance in designing highly efficient organic solar cells. Noncovalent intramolecular interactions have been often used for conformational control to enhance the planarity of polymers or molecules, which may reduce band gaps and promote charge transfer. However, it is not known if noncovalent interactions may alter the electronic properties of conjugated polymers through some mechanism other than the conformational control. Here, we studied the effects of various noncovalent interactions, including sulfur–nitrogen, sulfur–oxygen, sulfur–fluorine, oxygen–nitrogen, oxygen–fluorine, and nitrogen–fluorine, on the electronic properties of polymers with planar geometry using unconstrained and constrained density functional theory. We found that the sulfur–nitrogen intramolecular interaction may reduce the band gaps of polymers and enhance the charge transfer more obviously than other noncovalent interactions. Our findings are also consistent with the experimental data. For the first time, our study shows that the sulfur–nitrogen noncovalent interaction may further affect the electronic structure of coplanar conjugated polymers, which cannot be only explained by the enhancement of molecular planarity. Our work suggests a new mechanism to manipulate the electronic properties of polymers to design high-performance small-molecule-polymer and all-polymer solar cells.