Issiah B. Lozada
Donor-Acceptor Boron-Ketoiminate Complexes with Pendent N-Heterocyclic Arms: Switched-on Luminescence through N-Heterocycle Methylation
Lozada, Issiah B.; Ortiz, Robert J.; Braun, Jason D.; Williams, J.A. Gareth; Herbert, David E.
Authors
Robert J. Ortiz
Jason D. Braun
Professor Gareth Williams j.a.g.williams@durham.ac.uk
Professor
David E. Herbert
Abstract
A series of intramolecular, donor-stabilized BF2 complexes supported by phenanthridinyl-decorated, β-ketoiminate chelating ligand scaffolds is described, along with their characterization by spectroscopy and X-ray diffraction. In solution, the relative orientation of the pendent phenanthridinyl arm is fixed despite not coordinating to the boron center, and a well-resolved through-space interaction between a phenanthridinyl C–H and a single fluorine atom can be observed by 19F–1H NOE NMR spectroscopy. The neutral compounds are nonetheless only weakly luminescent in fluid solution, ascribed to nonradiative decay pathways enabled by rotation of the N-heterocyclic unit. Methylation of the phenanthridinyl nitrogen restricts this rotation, “switching on” comparably strong emission in solution. Modeling by density functional theory (DFT) and time-dependent DFT (TDDFT) indicates that the character of the lowest energy excitation changes upon methylation, with shallow calculated potential energy surfaces of the neutral complexes consistent with their lack of significant radiative decay.
Citation
Lozada, I. B., Ortiz, R. J., Braun, J. D., Williams, J. G., & Herbert, D. E. (2022). Donor-Acceptor Boron-Ketoiminate Complexes with Pendent N-Heterocyclic Arms: Switched-on Luminescence through N-Heterocycle Methylation. Journal of Organic Chemistry, 87(1), 184-196. https://doi.org/10.1021/acs.joc.1c02138
Journal Article Type | Article |
---|---|
Acceptance Date | Dec 8, 2021 |
Online Publication Date | Dec 22, 2021 |
Publication Date | Jan 7, 2022 |
Deposit Date | Mar 10, 2022 |
Publicly Available Date | Dec 22, 2022 |
Journal | Journal of Organic Chemistry |
Print ISSN | 0022-3263 |
Electronic ISSN | 1520-6904 |
Publisher | American Chemical Society |
Peer Reviewed | Peer Reviewed |
Volume | 87 |
Issue | 1 |
Pages | 184-196 |
DOI | https://doi.org/10.1021/acs.joc.1c02138 |
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Copyright Statement
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Organic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.joc.1c02138.
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