1,2,3,4‐Tetrafluorobiphenylene: A Prototype Janus‐Headed Scaffold for Ambipolar Materials

1,2,3,4‐Tetrafluorobiphenylene: A Prototype Janus‐Headed Scaffold for Ambipolar Materials Full article

Journal

ChemPlusChem
ISSN: 2192-6506

Output data

Year: 2024, Volume: 89, Number: 5, Article number : e202300692, Pages count : 10 DOI: 10.1002/cplu.202300692

Tags

ambipolar materials antiaromatics fluoroorganics structure and bonding synthesis

Authors

Nikulshin Pavel V. ^1,6 , Makarov Alexander Yu. ¹ , Koskin Igor P. ¹ , Becker Christina S. ¹ , Kazantzev Maksim S. ¹ , Beckmann Jens ² , Balmohammadi Yaser ³ , Grabowsky Simon ³ , Mebs Stefan ⁴ , Naumova Olga V. ⁵ , Protasov Dmitry Yu. ⁵ , Svit Kirill A. ⁵ , Irtegova Irina G. ¹ , Radiush Ekaterina A. ¹ , Bagryanskaya Irina Yu. ¹ , Shundrin Leonid A. ¹ , Zibarev Andrey V. ¹

Affiliations

1	N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry of Siberian Branch of Russian Academy of Sciences
2	University of Bremen
3	Department of Chemistry, Biochemistry and Pharmaceutical Science University of Bern3012 Bern, Switzerland
4	Institute for Experimental PhysicsFree University of Berlin14195 Berlin, Germany
5	Rzhanov Institute of Semiconductor Physics Siberian Branch of Russian Academy of Sciences
6	Topchiev Institute of Petrochemical Synthesis Russian Academy of Sciences

The title compound was synthesized by Ullmann cross-coupling in low yield as first representative of [n]phenylene containing hydrocarbon and fluorocarbon rings. Stille / Suzuki-Miyaura cross-coupling reactions, as well as substitution of fluorine in suitable starting compounds, failed to give the same product. The geometric and electronic structures of the title compound were studied by X-ray diffraction, cyclic voltammetry and density functional theory calculations, together with Hirshfeld surface and reduced density gradient analyses. The crystal structure features head-to-tail π-stacking and other fluorine-related secondary bonding interactions. From the nucleus-independent chemical shifts (NICS) descriptor, the four-membered ring of the title compound is antiaromatic, and the six-membered rings are aromatic. The Janus molecule is highly polarized; and the six-membered fluoro- and hydrocarbon rings are Lewis π-acidic and π-basic, respectively. The electrochemically-generated radical cation of the title compound is long-lived as characterized by electron paramagnetic resonance, whereas the radical anion is unstable in solution. The title compound reveals electrical properties of an insulator. On expanding its molecular scaffold towards partially fluorinated [n]phenylenes (n ≥ 2), the properties presumably can be transformed into those of semiconductors. In this context, the title compound is suggested as a prototype scaffold for ambipolar materials for organic electronics and spintronics.

Nikulshin P.V. , Makarov A.Y. , Koskin I.P. , Becker C.S. , Kazantzev M.S. , Beckmann J. , Balmohammadi Y. , Grabowsky S. , Mebs S. , Naumova O.V. , Protasov D.Y. , Svit K.A. , Irtegova I.G. , Radiush E.A. , Bagryanskaya I.Y. , Shundrin L.A. , Zibarev A.V.
1,2,3,4‐Tetrafluorobiphenylene: A Prototype Janus‐Headed Scaffold for Ambipolar Materials
ChemPlusChem. 2024. V.89. N5. e202300692 :1-10. DOI: 10.1002/cplu.202300692 WOS Scopus РИНЦ

Submitted:	Nov 26, 2023
Accepted:	Dec 5, 2023
Published print:	May 1, 2024

Web of science	WOS:001143273600001
Scopus	2-s2.0-85182452185
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