4.7 Article

Donor-Acceptor Boron-Ketoiminate Complexes with Pendent N-Heterocyclic Arms: Switched-on Luminescence through N-Heterocycle Methylation

期刊

JOURNAL OF ORGANIC CHEMISTRY
卷 87, 期 1, 页码 184-196

出版社

AMER CHEMICAL SOC
DOI: 10.1021/acs.joc.1c02138

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资金

  1. Natural Sciences Engineering Research Council of Canada [RGPIN-2014-03733]
  2. Canadian Foundation for Innovation [32146]
  3. Research Manitoba [32146]
  4. University of Manitoba

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A series of intramolecular, donor-stabilized BF2 complexes supported by phenanthridinyl-decorated, beta-ketoiminate chelating ligand scaffolds were characterized by spectroscopy and X-ray diffraction. The orientation of the phenanthridinyl arm in solution is fixed, despite not coordinating to the boron center, and a through-space interaction between phenanthridinyl C-H and a single fluorine atom was observed. Methylation of the phenanthridinyl nitrogen restricts rotation, leading to stronger emission in solution.
A series of intramolecular, donor-stabilized BF2 complexes supported by phenanthridinyl-decorated, beta-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 F-19-H-1 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.

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