Regulating Singlet-Triplet Energy Gaps through Substituent-Driven Modulation of the Exchange and Coulomb Interactions

Control of the singlet-triplet energy gap (ΔE_ST) is central to realizing productive energy conversion reactions, photochemical reaction trajectories, and emergent applications that exploit molecular spin physics. Despite this, no systematic methods have been defined to tune ΔE_ST in simple molecular frameworks, let alone by an approach that also holds chromophore size and electronic structural parameters (such as the HOMO-LUMO gap) constant. Using a combination of molecular design, photophysical and potentiometric experiments, and quantum chemical analyses, we show that the degree of electron-electron repulsion in excited singlet and triplet states may be finely controlled through the substitution pattern of a simple porphyrin absorber, enabling regulation of relative electronically excited singlet and triplet state energies by the designed restriction of the electron-electron Coulomb (J) and exchange (K) interaction magnitudes. This approach modulates the ΔE_ST magnitude by controlling the densities of state in the occupied and virtual molecular orbital manifolds, natural transition orbital polarization, and the relative contributions of one electron transitions involving select natural transition orbital pairs. This road map, which regulates electron density overlaps in the occupied and virtual states that define the singlet and triplet wave functions of these chromophores, enables new approaches to preserve excitation energy despite intersystem crossing.