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Structure-sensitive marker bands of metallocorroles: A resonance Raman study of manganese and gold corrole derivatives

Permanent lenke
https://hdl.handle.net/10037/26636
DOI
https://doi.org/10.1016/j.jinorgbio.2022.111783
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article.pdf (8.466Mb)
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Dato
2022-03-03
Type
Journal article
Tidsskriftartikkel
Peer reviewed

Forfatter
Terner, James; Kolle Ekaney, Thomas; Vazquez Lima, Hugo; Ghosh, Abhik
Sammendrag
Soret-excited resonance Raman spectra (λex 413.1 nm) were acquired for manganese(III) and gold(III) tris(pentafluorophenyl)corrole, each as four different isotopomeric samples: natural abundance, fully pyrrole-15N-substituted, fully meso13C-substituted, and fully pyrrole-15N-meso13C-substituted. The spectra were modeled with density functional theory-based vibrational analyses, which in general did an excellent job of reproducing both the absolute frequencies and isotope shifts. The results led to the assignment and visualization of approximately 10 prominent Raman bands. A key finding was that the bands could be categorized into two broad classes: Class A, exhibiting large 15N isotope shifts, assignable to vibrations with predominant Cα-N character, and Class B, exhibiting large meso13C isotope shifts, assignable to vibrations with predominant Cα-Cmeso character. Preliminary evidence suggests that the class A bands may serve as core size markers, while class B bands may correlate with the innocence or otherwise of the corrole macrocycle.
Forlag
Elsevier
Sitering
Terner, Kolle Ekaney, Vazquez Lima, Ghosh. Structure-sensitive marker bands of metallocorroles: A resonance Raman study of manganese and gold corrole derivatives. Journal of Inorganic Biochemistry. 2022;231
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