Positive shift in corrole redox potentials leveraged by modest beta-CF3-substitution helps achieve efficient photocatalytic C-H bond functionalization by group 13 complexes

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Tris- and tetrakis-beta-trifluoromethylated gallium (3CF(3)-Ga, 4CF(3)-Ga) and aluminum (3CF(3)-Al, 4CF(3)-Al) corrole systems were synthesized by a facile "one-pot" approach from the respective tri- and tetra-iodo starting compounds using the FSO2CF2CO2Me reagent. The isolated 5,10,15-(tris-pentafluorophenyl)corrole-based compounds set the groundwork for another important beta-substituent study in inorganic photocatalysis. As seen previously, -CF3 group substitution leads to red shifts in both the absorption and emission spectra compared to their unsubstituted counterparts (X. Zhan, et al., Inorg. Chem., 2019, 58, 6184-6198). All CF3-substituted corrole complexes showed strong fluorescence; 3CF(3)-Al possessed the highest fluorescence quantum yield (0.71) among these compounds. The photocatalytic production of bromophenol by way of these photosensitizing complexes was studied demonstrating that tris-trifluoromethylation is an important substitution class, especially when Ga3+ is present (experimental TON value in parentheses): 3CF(3)-Ga (192) > 4CF(3)-Ga (146) > 3CF(3)-Al (130) > 4CF(3)-Al (56) > 1-Ga (43) > 1-Al (18). The catalytic performance (turn-over number, TON) for benzylbromide formation (from toluene) was found to be: 3CF(3)-Ga (225) > 1-Ga (138) > 3CF(3)-Al (130) > 4CF(3)-Ga (126) > 1-Al (95) > 4CF(3)-Al (89); in these trials, benzaldehyde was also detected as a product in which 3CF(3)-Ga outperforms the other compounds (TON = 109). The tetra-CF3-substituted 4CF(3)-Ga and 4CF(3)-Al species exhibit a dramatic formal positive shift of 116 mV and 126 mV per [CF3] group, respectively, compared to the unsubstituted parent species 1-Ga and 1-Al. However, the absorbance values (lambda(abs) = 400 nm) of these corrole complexes (all equally concentrated: 4.0 x 10(-6) M) were 3CF(3)-Al (0.23) > 3CF(3)-Ga (0.22) > 1-Al (0.21) > 1-Ga (0.20) > 4CF(3)-Al (0.19) > 4CF(3)-Ga (0.15), which helps rationalize why 3CF(3)-Ga performs the best among these catalysts. These new photosensitizers were carefully characterized by H-1 and F-19 NMR spectroscopy to help verify the number and position (symmetry) of the CF3 groups; 3CF(3)-Ga and 3I-Al were structurally characterized. Distortions in the corrole macrocycle imposed by the multiple beta-substitution were quantified.
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DALTON TRANSACTIONS, v.48, no.32, pp.12279 - 12286

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CH-Journal Papers(저널논문)
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