Electronic and Spectroscopic Properties of Avobenzone Derivatives Attached to Mo Quadruple Bonds: Suppression of the Photochemical Enol-to-Keto Transformation.
From the reactions between Mo(TPB), where TPB 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-1λ³,2λ-dioxaborinin-4-yl)benzoic acid, HAvoBF, the compounds Mo(TPB)(Bzald), I; Mo(TPB)(A...
| Published in: | Journal of the American Chemical Society Vol. 137; no. 15; pp. 5155 - 5163 |
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| Main Authors: | , , , , , |
| Format: | Article |
| Published: |
American Chemical Society
4/22/2015
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| Subjects: | |
| Online Access: | View this record in EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=102560611&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 102560611 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 4/22/2015 vid: 137 iid: 15 pid: 997 pub: American Chemical Society artinfo: ui: 102560611 10.1021/jacs.5b01495 ppf: 5155 ppct: 8 formats: tig: atl: Electronic and Spectroscopic Properties of Avobenzone Derivatives Attached to Mo Quadruple Bonds: Suppression of the Photochemical Enol-to-Keto Transformation. aug: au: Chisholm, Malcolm H. Durr, Christopher B. Gustafson, Terry L. Render, William T. Spilker, Thomas F. Young, Philip J. affil: Department of Chemistry and Biochemistry, Ohio State University, 100 West 18th Avenue, Columbus, Ohio 43210, United States su: Molecular structure of ligands Electronic structure Emission spectroscopy Density functional theory Time-dependent density functional theory Benzoic acid sug: subj: Molecular structure of ligands Electronic structure Emission spectroscopy Density functional theory Time-dependent density functional theory Benzoic acid ab: From the reactions between Mo(TPB), where TPB 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-1λ³,2λ-dioxaborinin-4-yl)benzoic acid, HAvoBF, the compounds Mo(TPB)(Bzald), I; Mo(TPB)(Avo), II; and Mo(TPB)(AvoBF), III, have been isolated. Compounds I and II are red, and compound III is blue. The new compounds have been characterized by ³H 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 S states having lifetimes ~5-15 ps. The triplet states are Moδδ* 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 Mo unit shifts the ground state equilibrium entirely to the end form and quenches the degradation pathways of the avobenzone moiety. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2015 holdings: @attributes: islocal: N |
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