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Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
RESEARCH ARTICLE

Charge-transfer complexes of arylthiotetrathiafulvalenes and TCNQF4: their structural diversity and electronic states

Longfei Ma https://orcid.org/0000-0003-0444-2159 A * and Congjie Pan https://orcid.org/0000-0002-4896-7195 B
+ Author Affiliations
- Author Affiliations

A Department of Criminal Science and Technology, Henan Police College, Zhengzhou, 450046, P. R. China.

B School of Pharmacy, Henan University of Chinese Medicine, Zhengzhou, 450046, P. R. China.

* Correspondence to: malongfei@hnp.edu.cn

Handling Editor: Stuart Batten

Australian Journal of Chemistry 75(3) 174-180 https://doi.org/10.1071/CH21202
Submitted: 16 August 2021  Accepted: 17 November 2021   Published: 11 January 2022

© 2022 The Author(s) (or their employer(s)). Published by CSIRO Publishing.

Abstract

A series of charge-transfer (CT) complexes have been prepared via diffusion and evaporation methods comprising arylthio-substituted tetrathiafulvalene (Ar-S-TTF) derivatives 15 and TCNQF4. Crystallographic studies revealed the diverse crystal packing of the CT complexes, which is related to their flexible structure and the planar central cores of the Ar-S-TTF. The complexes could be divided into three systems according to the packing similarities and dissimilarities of Ar-S-TTF (donor, D) and TCNQF4 (acceptor, A), namely Class 1 (D on D and A on A segregated stacking), Class 2 ((–A–D–)n mixed stacking) and Class 3 (–D–D–D–D– and A, A stacks with each other in edge-to-face interactions between cations and anions). The presence of multiple intermolecular interactions promotes the formation of various stacking structures. There are two factors affecting the packing structures and compositions of the CT complexes: (1) the aryl groups thereon of Ar-S-TTF; and (2) the expanded π-conjugated system.

Keywords: arylthio-substituted tetrathiafulvalene, charge transfer, crystal packing, electrochemistry, electron donors, organic conductor, self-assembly, TCNQF4.


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