Molecular orbital node engineering in pyrene: linking chemical reactivity with room‑temperature phosphorescence

Abstract Substitutions at the nodal and anti-nodal positions of conjugated aromatics exert profound effects on their electronic properties, yet a systematic investigation is lacking on how these underlying quantum mechanical rules are manifested experimentally. Here, using polycyclic aromatic hydrocarbons derivatives as a model system, we systematically elucidate how nodal and anti-nodal substitutions dictate their chemical reactivity and physical properties. It is found that Sonogashira C–C coupling at the nodal position has a noticeably lower product yield than anti-nodal position under identical reflux conditions due to inhibited molecular orbital amplitude. Comprehensive spectroscopic characterization of the resulting substituted products reveals two striking photophysical differences: 1) Frontier orbital symmetry is largely conserved in node-substituted molecules, whereas the anti-nodal substitution induces strong symmetry-breaking, leading to accelerated fluorescence emission in anti-node-substituted pyrenes; 2) Nodal substitution induces the formation of charge-transfer states due to a twisted geometry, which activates room-temperature phosphorescence via improved singlet–triplet intersystem crossing. This study establishes an effective structure–property relationship linking molecular orbital symmetry to macroscopic cross-coupling reactivity and molecular photophysics within these conjugated aromatics.