DC Field | Value | Language |
---|---|---|
dc.contributor.author | Zhan, Xuan | ko |
dc.contributor.author | Yadav, Pinky | ko |
dc.contributor.author | Diskin-Posner, Yael | ko |
dc.contributor.author | Fridman, Natalia | ko |
dc.contributor.author | Sundararajan, Mahesh | ko |
dc.contributor.author | Ullah, Zakir | ko |
dc.contributor.author | Chen, Qiu-Cheng | ko |
dc.contributor.author | Shimon, Linda J. W. | ko |
dc.contributor.author | Mahammed, Atif | ko |
dc.contributor.author | Churchill, David G | ko |
dc.contributor.author | Baik, Mu-Hyun | ko |
dc.contributor.author | Gross, Zeev | ko |
dc.date.accessioned | 2019-09-10T02:20:31Z | - |
dc.date.available | 2019-09-10T02:20:31Z | - |
dc.date.created | 2019-09-09 | - |
dc.date.created | 2019-09-09 | - |
dc.date.issued | 2019-08 | - |
dc.identifier.citation | DALTON TRANSACTIONS, v.48, no.32, pp.12279 - 12286 | - |
dc.identifier.issn | 1477-9226 | - |
dc.identifier.uri | http://hdl.handle.net/10203/267429 | - |
dc.description.abstract | 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. | - |
dc.language | English | - |
dc.publisher | ROYAL SOC CHEMISTRY | - |
dc.title | Positive shift in corrole redox potentials leveraged by modest beta-CF3-substitution helps achieve efficient photocatalytic C-H bond functionalization by group 13 complexes | - |
dc.type | Article | - |
dc.identifier.wosid | 000480592500028 | - |
dc.identifier.scopusid | 2-s2.0-85070749981 | - |
dc.type.rims | ART | - |
dc.citation.volume | 48 | - |
dc.citation.issue | 32 | - |
dc.citation.beginningpage | 12279 | - |
dc.citation.endingpage | 12286 | - |
dc.citation.publicationname | DALTON TRANSACTIONS | - |
dc.identifier.doi | 10.1039/c9dt02150g | - |
dc.contributor.localauthor | Churchill, David G | - |
dc.contributor.localauthor | Baik, Mu-Hyun | - |
dc.contributor.nonIdAuthor | Zhan, Xuan | - |
dc.contributor.nonIdAuthor | Yadav, Pinky | - |
dc.contributor.nonIdAuthor | Diskin-Posner, Yael | - |
dc.contributor.nonIdAuthor | Fridman, Natalia | - |
dc.contributor.nonIdAuthor | Sundararajan, Mahesh | - |
dc.contributor.nonIdAuthor | Chen, Qiu-Cheng | - |
dc.contributor.nonIdAuthor | Shimon, Linda J. W. | - |
dc.contributor.nonIdAuthor | Mahammed, Atif | - |
dc.contributor.nonIdAuthor | Gross, Zeev | - |
dc.description.isOpenAccess | N | - |
dc.type.journalArticle | Article | - |
dc.subject.keywordPlus | SELECTIVE HALOGENATION | - |
dc.subject.keywordPlus | EXPANDED PORPHYRINS | - |
dc.subject.keywordPlus | OXYGENATION | - |
dc.subject.keywordPlus | BENZENE | - |
dc.subject.keywordPlus | ARYL | - |
dc.subject.keywordPlus | TRIFLUOROMETHYLATION | - |
dc.subject.keywordPlus | METALLOCORROLES | - |
dc.subject.keywordPlus | SUBSTITUTION | - |
dc.subject.keywordPlus | DIOXYGEN | - |
dc.subject.keywordPlus | HALIDES | - |
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