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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dc.contributor.authorZhan, Xuanko
dc.contributor.authorYadav, Pinkyko
dc.contributor.authorDiskin-Posner, Yaelko
dc.contributor.authorFridman, Nataliako
dc.contributor.authorSundararajan, Maheshko
dc.contributor.authorUllah, Zakirko
dc.contributor.authorChen, Qiu-Chengko
dc.contributor.authorShimon, Linda J. W.ko
dc.contributor.authorMahammed, Atifko
dc.contributor.authorChurchill, David Gko
dc.contributor.authorBaik, Mu-Hyunko
dc.contributor.authorGross, Zeevko
dc.date.accessioned2019-09-10T02:20:31Z-
dc.date.available2019-09-10T02:20:31Z-
dc.date.created2019-09-09-
dc.date.created2019-09-09-
dc.date.issued2019-08-
dc.identifier.citationDALTON TRANSACTIONS, v.48, no.32, pp.12279 - 12286-
dc.identifier.issn1477-9226-
dc.identifier.urihttp://hdl.handle.net/10203/267429-
dc.description.abstractTris- 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.-
dc.languageEnglish-
dc.publisherROYAL SOC CHEMISTRY-
dc.titlePositive shift in corrole redox potentials leveraged by modest beta-CF3-substitution helps achieve efficient photocatalytic C-H bond functionalization by group 13 complexes-
dc.typeArticle-
dc.identifier.wosid000480592500028-
dc.identifier.scopusid2-s2.0-85070749981-
dc.type.rimsART-
dc.citation.volume48-
dc.citation.issue32-
dc.citation.beginningpage12279-
dc.citation.endingpage12286-
dc.citation.publicationnameDALTON TRANSACTIONS-
dc.identifier.doi10.1039/c9dt02150g-
dc.contributor.localauthorChurchill, David G-
dc.contributor.localauthorBaik, Mu-Hyun-
dc.contributor.nonIdAuthorZhan, Xuan-
dc.contributor.nonIdAuthorYadav, Pinky-
dc.contributor.nonIdAuthorDiskin-Posner, Yael-
dc.contributor.nonIdAuthorFridman, Natalia-
dc.contributor.nonIdAuthorSundararajan, Mahesh-
dc.contributor.nonIdAuthorChen, Qiu-Cheng-
dc.contributor.nonIdAuthorShimon, Linda J. W.-
dc.contributor.nonIdAuthorMahammed, Atif-
dc.contributor.nonIdAuthorGross, Zeev-
dc.description.isOpenAccessN-
dc.type.journalArticleArticle-
dc.subject.keywordPlusSELECTIVE HALOGENATION-
dc.subject.keywordPlusEXPANDED PORPHYRINS-
dc.subject.keywordPlusOXYGENATION-
dc.subject.keywordPlusBENZENE-
dc.subject.keywordPlusARYL-
dc.subject.keywordPlusTRIFLUOROMETHYLATION-
dc.subject.keywordPlusMETALLOCORROLES-
dc.subject.keywordPlusSUBSTITUTION-
dc.subject.keywordPlusDIOXYGEN-
dc.subject.keywordPlusHALIDES-
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