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Mahesh Sundararajan
분자활성 촉매반응 연구단
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Maximizing Property Tuning of Phosphorus Corrole Photocatalysts through a Trifluoromethylation Approach

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Title
Maximizing Property Tuning of Phosphorus Corrole Photocatalysts through a Trifluoromethylation Approach
Author(s)
Xuan Zhan; Peter Teplitzky; Yael Diskin-Posner; Mahesh Sundararajan; Zakir Ullah; Qiu-Cheng Chen; Linda J. W. Shimon; Irena Saltsman; Atif Mahammed; Monica Kosa; Mu-Hyun Baik; David G. Churchill; Zeev Gross
Publication Date
2019-05
Journal
INORGANIC CHEMISTRY, v.58, no.9, pp.6184 - 6198
Publisher
AMER CHEMICAL SOC
Abstract
An eight-member series of CF 3 -substituted difluorophosphorus corroles was prepared for establishing a structure-activity profile of these high-potential photosensitizers. It consisted of preparing all four possible isomers of the monosubstituted corrole and complexes with 2-, 3-, 4-, and 5-CF 3 groups on the macrocycle's periphery. The synthetic pathway to these CF 3 -substituted derivatives, beginning with (tpfc)PF 2 , involves two different initial routes: (i) direct electrophilic CF 3 incorporation using FSO 2 CF 2 CO 2 Me and copper iodide, or (ii) bromination to achieve the 2,3,8,17,18-pentabrominated compound using excess bromine in methanol. Crystallographic investigations revealed that distortion of the original planar macrocycle is evident even in the monosubstituted case and that it becomes truly severe for the penta-CF 3 -substituted derivative 5. There is a shift in redox potentials of about 193 mV per -CF 3 group, which decreases to only 120 mV for the fifth one in 5. Differences in the electronic spectra suggest that the Gouterman four orbital model decreases in relevance upon gradual -CF 3 substitution, a conclusion that was corroborated by DFT calculations. The very significant energy lowering of the frontier orbitals suggested that photoexcitation should lead to a highly oxidizing photocatalyst. This hypothesis was proven true by finding that the most synthetically accessible CF 3 -substituted derivative is an excellent catalyst for the photoinduced conversion of bromide to bromine (phenol, toluene, and benzene assay) © 2019 American Chemical Society.
URI
https://pr.ibs.re.kr/handle/8788114/5852
ISSN
0020-1669
Appears in Collections:
Center for Catalytic Hydrocarbon Functionalizations(분자활성 촉매반응 연구단) > Journal Papers (저널논문)
Files in This Item:
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