Issue 26, 2025

Activation of chalcogen bonding in tetrathiafulvalene derivatives with Se/S differentiation

Abstract

Activation of σ-holes on selenium atoms through the oxidation of the tetrathiafulvalene core in selenomethyl-substituted TTFs was evaluated in comparison with the less activatable thiomethyl moieties in 4,5-bis(methylseleno)-4′,5′-bis(methylthio)-tetrathiafulvalene 1. Three charge-transfer complexes with TCNQ, TCNQF and TCNQF2 were structurally characterized, with all of them showing a partial degree of charge transfer, ρ, in the range of ±0.5–±0.6, with alternating stacks of DDAADDAA patterns with TCNQ and DADADA patterns with TCNQF and TCNQF2. No ChB interactions were identified in the latter two co-crystals, where MeSe and MeS- were disordered in 50 : 50 distribution, as also observed in the structure of neutral 1. Alternatively, in the co-crystal with TCNQ, dissymmetric Se/S distribution (69 : 31) was associated with a strong Se⋯NC ChB interaction involving the majority Se atom. A similar preferential ChB interaction with Se was observed in the perchlorate salt (1)ClO4, where the majority Se atom (71 : 29 Se/S distribution) interacts through Se⋯O ChB with the ClO4 anion.

Graphical abstract: Activation of chalcogen bonding in tetrathiafulvalene derivatives with Se/S differentiation

Supplementary files

Article information

Article type
Paper
Submitted
23 Apr 2025
Accepted
29 May 2025
First published
03 Jun 2025
This article is Open Access
Creative Commons BY-NC license

New J. Chem., 2025,49, 11501-11508

Activation of chalcogen bonding in tetrathiafulvalene derivatives with Se/S differentiation

M. Beau, I. Jeon, O. Jeannin, T. Guizouarn and M. Fourmigué, New J. Chem., 2025, 49, 11501 DOI: 10.1039/D5NJ01745A

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. You can use material from this article in other publications, without requesting further permission from the RSC, provided that the correct acknowledgement is given and it is not used for commercial purposes.

To request permission to reproduce material from this article in a commercial publication, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party commercial publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements