title: Electronic and Spectroscopic Properties of Avobenzone Derivatives Attached to Mo₂ Quadruple Bonds: Suppression of the Photochemical Enol-to-Keto Transformation.
abstract: 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 ∼5-15 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.
authors: Department of Chemistry and Biochemistry, The Ohio State University, 100 West 18th Avenue, Columbus, Ohio 43210, United States.
authors: Malcolm H
authors: MH
authors: Chisholm
authors: Department of Chemistry and Biochemistry, The Ohio State University, 100 West 18th Avenue, Columbus, Ohio 43210, United States.
authors: Christopher B
authors: CB
authors: Durr
authors: Department of Chemistry and Biochemistry, The Ohio State University, 100 West 18th Avenue, Columbus, Ohio 43210, United States.
authors: Terry L
authors: TL
authors: Gustafson
authors: Department of Chemistry and Biochemistry, The Ohio State University, 100 West 18th Avenue, Columbus, Ohio 43210, United States.
authors: William T
authors: WT
authors: Kender
authors: Department of Chemistry and Biochemistry, The Ohio State University, 100 West 18th Avenue, Columbus, Ohio 43210, United States.
authors: Thomas F
authors: TF
authors: Spilker
authors: Department of Chemistry and Biochemistry, The Ohio State University, 100 West 18th Avenue, Columbus, Ohio 43210, United States.
authors: Philip J
authors: PJ
authors: Young
mesh_terms: D000438:Alcohols / Q000737:chemistry*; D018360:Crystallography, X-Ray; D004583:Electrons; D007659:Ketones / Q000138:chemical synthesis* / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D013058:Mass Spectrometry; D008958:Models, Molecular; D015394:Molecular Structure; D008982:Molybdenum / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D055668:Photochemical Processes; D011427:Propiophenones / Q000737:chemistry*; D011522:Protons; D013055:Spectrophotometry, Infrared; D013056:Spectrophotometry, Ultraviolet; D013997:Time Factors
chemical_list: D000438:Alcohols; D007659:Ketones; D009942:Organometallic Compounds; D011427:Propiophenones; D011522:Protons; D008982:Molybdenum; C049935:avobenzone