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Air- and photo-stable luminescent carbodicarbene-azaboraacenium ions

Nature Chemistry volume 16, pages 437–445 (2024)Cite this article

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Abstract

Substitution of a C=C bond by an isoelectronic B–N bond is a well-established strategy to alter the electronic structure and stability of acenes. BN-substituted acenes that possess narrow energy gaps have attractive optoelectronic properties. However, they are susceptible to air and/or light. Here we present the design, synthesis and molecular structures of fully π-conjugated cationic BN-doped acenes stabilized by carbodicarbene ligands. They are luminescent in the solution and solid states and show high air and moisture stability. Compared with their neutral BN-substituted counterparts as well as the parent all-carbon acenes, these species display improved quantum yields and small optical gaps. The electronic structures of the azabora-anthracene and azabora-tetracene cations resemble higher-order acenes while possessing high photo-oxidative resistance. Investigations using density functional theory suggest that the stability and photo-physics of these conjugated systems may be ascribed to their cationic nature and the electronic properties of the carbodicarbene.

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Fig. 1: Carbonaceous acenes, cationic BN-doped PAHs and azaboraacenium ions.
Fig. 2: Synthesis and single-crystal structures of azaboraacenium ions.
Fig. 3: Electronic structures.
Fig. 4: Optoelectronic properties.
Fig. 5: Stability evaluation.

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Data availability

Crystallographic data for the structures reported in this article have been deposited at the Cambridge Crystallographic Data Centre, under deposition numbers CCDC 2225725 (1a), 2225726 (1b), 2225727 (2a), 2225728 (2b), 2225729 (3a), 2225730 (3b) and 2225731 (7). Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/. All other relevant data generated and analysed during this study, which include experimental, spectroscopic, crystallographic and computational data, are included in this article and its Supplementary Information. Source data are provided with this paper.

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Acknowledgements

We are grateful to the Arnold and Mabel Beckman Foundation for support of this work through a Beckman Young Investigator award (R.J.G.). The National Science Foundation Major Research Instrumentation (CHE 2018870) programme is also acknowledged (Bruker D8 Venture single crystal X-ray diffractometer). The University of Virginia (Rivanna) and Massachusetts Institute of Technology (Engaging, SuperCloud) High Performance Computing clusters provided computational resources and technical support that have contributed to the results reported herein.

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Authors and Affiliations

  1. Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA, USA

    Chun-Lin Deng, Bi Youan E. Tra, Samir Kumar Sarkar & Robert J. Gilliard Jr.

  2. Department of Chemistry, University of Virginia, Charlottesville, VA, USA

    Akachukwu D. Obi & Diane A. Dickie

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  1. Chun-Lin Deng
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Contributions

C.-L.D. and R.J.G. conceived and designed the project. C.-L.D. performed the experimental work as well as the theoretical studies. C.-L.D. and R.J.G. analysed the data. A.D.O. assisted in the synthetic experiments. B.Y.E.T. conducted the elemental analysis. S.K.S. provided the NHC ligand used in the experiments. D.A.D. and A.D.O. carried out the crystallographic data collection and refinement. C.-L.D. wrote the original draft, and R.J.G. edited with input from all authors. R.J.G. directed and supervised the research.

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Correspondence to Robert J. Gilliard Jr..

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Competing interests

C.-L.D., R.J.G., A.D.O. and S.K.S. are inventors on a provisional patent filed by the University of Virginia on the synthesis and properties of luminescent carbodicarbene-azaboraacenium ions.

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Nature Chemistry thanks Samuel Guieu and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–116, Table 1–14, detailed synthetic procedures and NMR spectra for all compounds, crystallographic, photophysical, spectroscopic studies and computational details.

Supplementary Data 1

Crystallographic data for compound 1a, CCDC 2225725.

Supplementary Data 2

Crystallographic data for compound 1b, CCDC 2225726.

Supplementary Data 3

Crystallographic data for compound 2a, CCDC 2225727.

Supplementary Data 4

Crystallographic data for compound 2b, CCDC 2225728.

Supplementary Data 5

Crystallographic data for compound 3a, CCDC 2225729.

Supplementary Data 6

Crystallographic data for compound 3b, CCDC 2225730.

Supplementary Data 7

Crystallographic data for compound 7, CCDC 2225731.

Supplementary Data 8

Cartesian coordinates of optimized and calculated structures.

Supplementary Data 9

Source data for Supplementary Fig. 29, 30, 31, 32, 108b, 110b and 111b.

Source data

Source Data Fig. 5b

Numerical source data for Fig. 5b.

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Deng, CL., Obi, A.D., Tra, B.Y.E. et al. Air- and photo-stable luminescent carbodicarbene-azaboraacenium ions. Nat. Chem. 16, 437–445 (2024). https://doi.org/10.1038/s41557-023-01381-0

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