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Yin H, Carroll PJ, Manor BC, et al. Cerium Photosensitizers: Structure-Function Relationships and Applications in Photocatalytic Aryl Coupling Reactions. J Am Chem Soc. 2016;138(18):5984-93doi: 10.1021/jacs.6b02248.
Yin, H., Carroll, P. J., Manor, B. C., Anna, J. M., & Schelter, E. J. (2016). Cerium Photosensitizers: Structure-Function Relationships and Applications in Photocatalytic Aryl Coupling Reactions. Journal of the American Chemical Society, 138(18), 5984-93. https://doi.org/10.1021/jacs.6b02248
Yin, Haolin, et al. "Cerium Photosensitizers: Structure-Function Relationships and Applications in Photocatalytic Aryl Coupling Reactions." Journal of the American Chemical Society vol. 138,18 (2016): 5984-93. doi: https://doi.org/10.1021/jacs.6b02248
Yin H, Carroll PJ, Manor BC, Anna JM, Schelter EJ. Cerium Photosensitizers: Structure-Function Relationships and Applications in Photocatalytic Aryl Coupling Reactions. J Am Chem Soc. 2016 May 11;138(18):5984-93. doi: 10.1021/jacs.6b02248. Epub 2016 May 02. PMID: 27058605.
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J Am Chem Soc. 2016 May 11;138(18):5984-93. doi: 10.1021/jacs.6b02248. Epub 2016 May 02.

Cerium Photosensitizers: Structure-Function Relationships and Applications in Photocatalytic Aryl Coupling Reactions.

Journal of the American Chemical Society

Haolin Yin, Patrick J Carroll, Brian C Manor, Jessica M Anna, Eric J Schelter

Affiliations

  1. P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania , 231 South 34 Street, Philadelphia, Pennsylvania 19104, United States.

PMID: 27058605 DOI: 10.1021/jacs.6b02248

Abstract

Two complete mixed-ligand series of luminescent Ce(III) complexes with the general formulas [(Me3Si)2NC(N(i)Pr)2]xCe(III)[N(SiMe3)2]3-x (x = 0, 1-N; x = 1, 2-N, x = 2, 3-N; x = 3, 4) and [(Me3Si)2NC(N(i)Pr)2]xCe(III)(OAr)3-x (x = 0, 1-OAr; x = 1, 2-OAr, x = 2, 3-OAr; x = 3, 4) were developed, featuring photoluminescence quantum yields up to 0.81(2) and lifetimes to 117(1) ns. Although the 4f → 5d absorptive transitions for these complexes were all found at ca. 420 nm, their emission bands exhibited large Stokes shifts with maxima occurring at 553 nm for 1-N, 518 nm for 2-N, 508 nm for 3-N, and 459 nm for 4, featuring yellow, lime-green, green, and blue light, respectively. Combined time-dependent density functional theory (TD-DFT) calculations and spectroscopic studies suggested that the long-lived (2)D excited states of these complexes corresponded to singly occupied 5dz(2) orbitals. The observed difference in the Stokes shifts was attributed to the relaxation of excited states through vibrational processes facilitated by the ligands. The photochemistry of the sterically congested complex 4 was demonstrated by C-C bond forming reaction between 4-fluoroiodobenzene and benzene through an outer sphere electron transfer pathway, which expands the capabilities of cerium photosensitizers beyond our previous results that demonstrated inner sphere halogen atom abstraction reactivity by 1-N.

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