Experimental Evidence for a Triplet Biradical Excited-State Mechanism in the Photoreactivity of N,C-Chelate Organoboron Compounds.

N,C-chelate organoborates represent an emerging class of photoresponsive materials due to their photochromic switching at a boron center. Despite the promising applicability of such systems, little is known about the excited-state processes that lead to their unique photoreactivity, which is detrimental to the design of next-generation smart materials based on boron. As part of our ongoing effort to understand and improve the utility of these organoboron compounds, we report some of the first experimental evidence to support an excited-state mechanism for N,C-chelate organoborates. Femtosecond transient absorption spectroscopy combined with steady-state UV/vis and fluorescence measurements gives direct insight into their underlying photochemical processes, such as the formation of a common triplet charge-transfer state which either relaxes radiatively or undergoes the desired photoisomerization through a biradical intermediate. With this information, a complete mechanistic picture of the excited-state reactivity of N,C-chelate organoborates has been established, which is anticipated to lead to new smart materials with improved performance.

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