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RISS 인기검색어
- 검색키워드
- 저자 : Saltsman, Irena (검색결과 1 건)
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Zhan, Xuan,Teplitzky, Peter,Diskin-Posner, Yael,Sundararajan, Mahesh,Ullah, Zakir,Chen, Qiu-Cheng,Shimon, Linda J. W.,Saltsman, Irena,Mahammed, Atif,Kosa, Monica,Baik, Mu-Hyun,Churchill, David G.,Gros ACS AMERICAN CHEMICAL SOCIETY 2019 Inorganic Chemistry Vol.58 No.9
<P>An eight-member series of CF<SUB>3</SUB>-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<SUB>3</SUB> groups on the macrocycle’s periphery. The synthetic pathway to these CF<SUB>3</SUB>-substituted derivatives, beginning with (<B>tpfc</B>)<B>PF</B><SUB><B>2</B></SUB>, involves two different initial routes: (i) direct electrophilic CF<SUB>3</SUB> incorporation using FSO<SUB>2</SUB>CF<SUB>2</SUB>CO<SUB>2</SUB>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<SUB>3</SUB>-substituted derivative <B>5</B>. There is a shift in redox potentials of about 193 mV per -CF<SUB>3</SUB> group, which decreases to only 120 mV for the fifth one in <B>5</B>. Differences in the electronic spectra suggest that the Gouterman four orbital model decreases in relevance upon gradual -CF<SUB>3</SUB> 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<SUB>3</SUB>-substituted derivative is an excellent catalyst for the photoinduced conversion of bromide to bromine (phenol, toluene, and benzene assay).</P><P>CF<SUB>3</SUB>-substituted difluorophosphorus corroles were synthesized and studied by CV, NMR spectroscopy, crystallography, and DFT. All four possible isomers of the monosubstituted corrole and complexes with 2-, 3-, 4-, and 5-CF<SUB>3</SUB> groups on the macrocycle’s periphery were prepared. The sterical and electronic role of the -CF<SUB>3</SUB> unit became evident through the study of the 5-CF<SUB>3</SUB> species which was found to be an excellent bromide photocatalyst (photoxidation with phenol, toluene, and benzene assays).</P> [FIG OMISSION]</BR>
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