Estimation of Heisenberg exchange interaction in rigid photoexcited chromophore-radical compound by transient EPR.

The magnetic field dependence of the spin polarization in a photoexcited rigid chromophore-radical conjugate is theoretically investigated. The excitation of the chromophore-radical conjugate often populates the metastable doublet and quartet states formed by the interactions of the unpaired electrons of the triplet chromophore and the radical. The intensities of the +1/2 ↔ - 1/2 transitions of the doublet and quartet manifolds are sensitive to the ratio jω = 3J/ω0 between the triplet-doublet exchange interaction J and the Zeeman energy ω0. It is shown that the analytical expressions of these intensities previously found for the triplet mechanism of the initial spin polarization can be expanded and applied to a broader class of compounds that may have other intersystem crossing pathways of the depopulation of the excited singlet state of the chromophore. It is also shown that the exchange interaction can be evaluated not only by comparing the electron paramagnetic resonance spectra obtained in different microwave frequency bands but also by comparing the data obtained in the same microwave band but with a shift of the frequency of the resonator. The results obtained broaden the potential applications of the previously proposed approach for analyzing the correlation between the exchange coupling and the distance separating the radical and the chromophore spins, as well as the structure of the bridge connecting their fragments.

A Rational Way to Control the Triplet State Wave Function Confinement of Organic Chromophores: Effect of the Connection Sites and Spin Density Distribution-Guided Molecular Structure Design Principles in Bodipy Dimers.

To study the intersystem crossing (ISC) and the spatial confinement of the triplet excited states of organic chromophores, we prepared a series of Bodipy dimers. We found that the connection position of the two units has a significant effect on the absorption and fluorescence. Singlet oxygen quantum yields of 3.8-12.4% were observed for the dimers, which are independent of solvent polarity. Nanosecond transient absorption spectra indicate the population of long-lived triplet excited states with lifetimes (τT) of 45-454 µs. Pulsed laser-excited time-resolved electron paramagnetic resonance (TREPR) spectra show that the T1 triplet states are essentially delocalized, which is different from the case for the previously reported Bodipy dimers. The TREPR spectra of the triplet states imply that the delocalization over the whole dimer essentially depends on the electron density of the carbon atoms at the connection sites. This property may become a universal rule for controlling the T1 state confinement in multichromophore organic molecules.