Electronic and Spectroscopic Properties of Avobenzone Derivatives Attached to Mo2 Quadruple Bonds: Suppression of the Photochemical Enol-to-Keto Transformation.
J Am Chem Soc
; 137(15): 5155-62, 2015 Apr 22.
Article
en En
| MEDLINE
| ID: mdl-25856290
From the reactions between Mo2(T(i)PB)4, where T(i)PB is 2,4,6-triisopropylbenzoate, and 2 equiv of the acids 4-formylbenzoic acid, HBzald; 4-(3-oxo-3-phenylpropanoyl)benzoic acid, HAvo; and 4-(2,2-difluoro-6-phenyl-2H-1λ(3),3,2λ(4)-dioxaborinin-4-yl)benzoic acid, HAvoBF2, the compounds Mo2(T(i)PB)2(Bzald)2, I; Mo2(T(i)PB)2(Avo)2, II; and Mo2(T(i)PB)2(AvoBF2)2, III, have been isolated. Compounds I and II are red, and compound III is blue. The new compounds have been characterized by (1)H NMR, MALDI-TOF MS, steady-state absorption and emission spectroscopies, and femtosecond and nanosecond time-resolved transient absorption and infrared spectroscopies. Electronic structure calculations employing density functional theory and time-dependent density functional theory have been carried out to aid in the interpretation of these data. These compounds have strong metal-to-ligand charge transfer, MLCT, and transitions in the visible region of their spectra, and these comprise the S1 states having lifetimes â¼5-15 ps. The triplet states are Mo2δδ* with lifetimes in the microseconds. The spectroscopic properties of I and II are similar, whereas the planarity of the ligand in III greatly lowers the energy of the MLCT and enhances the intensity of the time-resolved spectra. The Mo2 unit shifts the ground state equilibrium entirely to the enol form and quenches the degradation pathways of the avobenzone moiety.
Texto completo:
1
Colección:
01-internacional
Base de datos:
MEDLINE
Asunto principal:
Compuestos Organometálicos
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Propiofenonas
/
Alcoholes
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Cetonas
/
Molibdeno
Tipo de estudio:
Prognostic_studies
Idioma:
En
Revista:
J Am Chem Soc
Año:
2015
Tipo del documento:
Article
País de afiliación:
Estados Unidos
Pais de publicación:
Estados Unidos