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RESEARCH PRODUCT

Distinct Photophysics of the Isomers of B18H22 Explained

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The photophysics of the two isomers of octadecaborane(22), anti- and syn-B 18H 22, have been studied by UV-vis spectroscopic techniques and theoretical computational methods. In air-saturated hexane, anti-B 18H 22 shows fluorescence with a high quantum yield, Φ F = 0.97, and singlet oxygen O 2( 1Δ g) production (Φ Δ ∼ 0.008). Conversely, isomer syn-B 18H 22 shows no measurable fluorescence, instead displaying much faster, picosecond nonradiative decay of excited singlet states. Computed potential energy hypersurfaces (PEHs) for both isomers rationalize these data, pointing to a deep S 1 minimum for anti-B 18H 22 and a conical intersection (CI) between its S 0 and S 1 states that lies 0.51 eV higher in energy. Such an energy barrier to nonradiative relaxation is not present in the PEH of syn-B 18H 22, and the system therefore has sufficient initial energy on excitation to reach the (S 0/S 1) CI and to then decay to the ground state without fluorescence. The computational analysis of the geometries at stationary points along the PEH of both isomers shows that the determining factor for the dissimilar photophysics of anti- and syn-B 18H 22 may be due to the significant differences in the geometrical rearrangements at their respective conical intersections. Thus, the syn isomer shows one very large, B-B elongation of 1.2 Å from 1.8 Å in the ground state to 3.0 Å at the CI, whereas the anti isomer shows smaller elongations (below 1 Å) in several B-B connectivities at its (S 0/S 1) CI. The absorbed energy in S 1 for the anti-B 18H 22 is therefore redistributed vibrationally into several regions of the molecule rather than almost completely into a single vibrational mode as in the case for the syn isomer. The consequent prolonged S 1 lifetime for the anti isomer allows for relaxation via fluorescence. © 2012 American Chemical Society.