Azulene-Fused Acenes
Albert Ong
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543 Singapore
Search for more papers by this authorProf. Tao Tao
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543 Singapore
School of Chemistry and Materials Science, Nanjing University of Information Science & Technology, Nanjing, 210044 P. R. China
Search for more papers by this authorCorresponding Author
Dr. Qing Jiang
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543 Singapore
Search for more papers by this authorDr. Yi Han
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543 Singapore
Search for more papers by this authorDr. Yaping Ou
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543 Singapore
Search for more papers by this authorProf. Kuo-Wei Huang
KAUST Catalysis Center and Division of Physical Science and Engineering, King Abdullah University of Science and Technology, Thuwal, 23955-6900 Saudi Arabia
Search for more papers by this authorCorresponding Author
Prof. Chunyan Chi
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543 Singapore
Search for more papers by this authorAlbert Ong
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543 Singapore
Search for more papers by this authorProf. Tao Tao
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543 Singapore
School of Chemistry and Materials Science, Nanjing University of Information Science & Technology, Nanjing, 210044 P. R. China
Search for more papers by this authorCorresponding Author
Dr. Qing Jiang
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543 Singapore
Search for more papers by this authorDr. Yi Han
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543 Singapore
Search for more papers by this authorDr. Yaping Ou
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543 Singapore
Search for more papers by this authorProf. Kuo-Wei Huang
KAUST Catalysis Center and Division of Physical Science and Engineering, King Abdullah University of Science and Technology, Thuwal, 23955-6900 Saudi Arabia
Search for more papers by this authorCorresponding Author
Prof. Chunyan Chi
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543 Singapore
Search for more papers by this authorGraphical Abstract
Fusion of azulene to acenes of various length led to unexpected properties such as aromaticity and photophysical properties, and they are more stable than the respective isoelectronic acenes. Their dications showed aromaticity shift and one of them exhibited open-shell diradical character.
Abstract
Non-alternant non-benzenoid π-conjugated polycyclic hydrocarbons (PHs) are expected to exhibit very different electronic properties from the all-benzenoid PHs. Herein, we report the synthesis and physical properties of three azulene-fused acene molecules (1, 2 and 3), which are isoelectronic to the pentacene, hexacene and heptacene, respectively. X-ray crystallographic analysis, NMR spectra, and theoretical calculations reveal a localised aromatic backbone comprising all the six- and five-membered rings while the seven-membered ring remains non-aromatic. They display properties of both azulene and acenes and are much more stable than the respective acenes. The dications of 1, 2 and 3 were formed by chemical oxidation. Notably, 32+ exhibited an open-shell diradical character (y0=30.2 %) as confirmed by variable-temperature NMR and ESR measurements, which can be explained by recovery of aromaticity of an 2,6-anthraquinodimethane unit annulated with two aromatic tropylium rings.
Conflict of interest
The authors declare no conflict of interest.
Open Research
Data Availability Statement
The data that support the findings of this study are available in the supplementary material of this article.
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| anie202209286-sup-0001-Molecule_1.cif933.9 KB | Supporting Information |
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