4.8 Article

Air-Stable Thermoluminescent Carbodicarbene-Borafluorenium Ions

Journal

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 144, Issue 1, Pages 590-598

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/jacs.1c11861

Keywords

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Funding

  1. University of Virginia (UVA)
  2. National Science Foundation [CHE 2046544, CHE 2018870]
  3. Alfred P. Sloan Foundation
  4. Beckman Young Investigator award from the Arnold & Mabel Beckman Foundation
  5. NIH [OD016446]

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This article reports the synthesis, molecular structures, and optical properties of a new class of air-stable borenium ions stabilized by the strongly donating carbodicarbene ligand. These ions exhibit thermoluminescence in solution and increased quantum yields in the solid state, with the ability to emit white light at lower temperatures. The effect of anion size and ligand rotation on the optical properties is also investigated, complemented by theoretical analysis of the excited-state dynamics.
Borenium ions, originally synthesized as fundamentally important laboratory curiosities, have attracted significant attention due to their applications in catalysis and frustrated Lewis pair chemistry. However, investigations of the materials properties of these types of compounds are exceptionally rare. Herein, we report the synthesis, molecular structures, and optical properties of a new class of air-stable borenium ions, stabilized by the strongly donating carbodicarbene (CDC) ligand (2, 3, 6). Notably, CDC-borafluorenium ions exhibit thermoluminescence in solution, a result of a twisted intramolecular charge transfer process. The temperature responsiveness, which is observable by the naked eye, is assessed over a 20 to -60 degrees C range. Significantly, compound 2 emits white light at lower temperatures. In the solid state, these borocations exhibit increased quantum yields due to aggregation-induced emission. CDC-borafluorenium ions with two different counteranions (Br-, BPh4-) were investigated to evaluate the effect of anion size on the solution and solid-state optical properties. In addition, CDCs containing both symmetrical and unsymmetrical N-heterocycles (bis(1-isopropyl-3-methylbenzimidazol-2-ylidene)methane and bis(1,3-dimethyl-1,3-dihydro-2H-benzo[d]imidazol-2-ylidene)methane) were tested to understand the implications of free rotation about the CDC ligand carbon-carbon bonds. The experimental work is complemented by a comprehensive theoretical analysis of the excited-state dynamics.

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