Direct observation of the geometries of excited states and metastable intermediates can be accomplished by monitoring photochemical reactions in real time by X-ray diffraction. We are applying this technique to capture critical intermediates in energy conversion processes. Of current focus are those intermediates that promote HX splitting, which is limited by the efficiency of M�X bond activation and X�X elimination. Using X-ray photocrystallography, we have observed that a M(�-X)M�X bridging intermediate is critical to halogen elimination from binuclear metal cores. With this result as a guidepost, the time-resolved kinetics for M�X activation and X elimination may be unraveled. The combination of time-resolved X-ray and kinetics experiments provides a powerful platform from which to delineate energy conversion pathways.

Use of photocrystallography to capture critical intermediates in HX energy conversion photocycles

247th National Meeting (2014)

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