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

Nikulshin, Pavel V; Makarov, Alexander Yu; Koskin, Igor P; Becker, Christina S; Kazantzev, Maksim S; Beckmann, Jens; Balmohammadi, Yaser; Grabowsky, Simon; Mebs, Stefan; Naumova, Olga V; Protasov, Dmitry Yu; Svit, Kirill A; Irtegova, Irina G; Radiush, Ekaterina A; Bagryanskaya, Irina Yu; Shundrin, Leonid A; Zibarev, Andrey V (2024). 1,2,3,4-Tetrafluorobiphenylene: A Prototype Janus-Headed Scaffold for Ambipolar Materials. ChemPlusChem, 89(5), e202300692. Wiley 10.1002/cplu.202300692

[img] Text
ChemPlusChem_-_2023_-_Nikulshin_-_1_2_3_4_Tetrafluorobiphenylene__A_Prototype_Janus_Headed_Scaffold_for_Ambipolar_Materials.pdf - Accepted Version
Restricted to registered users only until 5 December 2024.
Available under License Publisher holds Copyright.

Download (3MB) | Request a copy

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.

Item Type:

Journal Article (Original Article)


08 Faculty of Science > Department of Chemistry, Biochemistry and Pharmaceutical Sciences (DCBP)

UniBE Contributor:

Balmohammadi, Yaser, Grabowsky, Simon


500 Science > 570 Life sciences; biology
500 Science > 540 Chemistry








Pubmed Import

Date Deposited:

06 Dec 2023 14:37

Last Modified:

16 May 2024 00:12

Publisher DOI:


PubMed ID:


Uncontrolled Keywords:

Antiaromatics Electrochemistry Fluoroorganics Synthesis, Structure and Bonding organic semiconductors





Actions (login required)

Edit item Edit item
Provide Feedback