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Semiconductive 2D arrays of pancake-bonded oligomers of partially charged TCNQ radicals

Molčanov, Krešimir; Milašinović, Valentina; Kojić-Prodić, Biserka; Maltar-Strmečki, Nadica; You, Jiangyang; Šantić, Ana; Kanižaj, Lidija; Stilinović, Vladimir; Fotović, Luka (2022) Semiconductive 2D arrays of pancake-bonded oligomers of partially charged TCNQ radicals. IUCrJ, 9 (4). pp. 449-467. ISSN 2052-2525

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Multicentre two-electron (mc/2e or pancake bonding) bonding between 7, 7, 8, 8- tetracyanoquinodimethane (TCNQ) radical anions was studied on its 14 novel salts with planar organic cations. Formal charges of the TCNQδ− moieties are −1/2 and −2/3, and they form mc/2e bonded dimers, trimers and tetramers which are further stacked into extended arrays. Multicentre bonding within these oligomers is characterised by short interplanar separations of 2.9 − 3.2 Å ; distances between the oligomers are larger, typically > 3.3 Å. The stacks are laterally connected by C−H···N hydrogen bonding, forming 2D arrays. The nature of mc/2e bonding is characterised by structural, magnetic and electrical data. The compounds are found to be semiconductors, and high conductivity [10-2 Scm-1] correlates with short interplanar distances between pancake-bonded oligomers.

Item Type: Article
Uncontrolled Keywords: multicentre two-electron bonding ; TCNQ radical anion ; crystal structure ; crystal engineering ; magnetic properties ; electrical properties
Subjects: NATURAL SCIENCES > Chemistry
Divisions: Division of Materials Chemistry
Division of Materials Physics
Division of Physical Chemistry
Project titleProject leaderProject codeProject type
Multicentrične kovalentne veze i pi-interakcije određuju fizička svojstva kristala organskih radikalaMolčanov, KrešimirIP-2019-04-4674HRZZ
Depositing User: Krešimir Molčanov
Date Deposited: 03 Apr 2023 13:23
DOI: 10.1107/s2052252522004717

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