Charge activation of chalcogen bonding interactions in a bis(selenomethyl)-substituted tetrathiafulvalene and its salts
Abstract
The preparation, crystal structure and electrochemical properties of a novel tetrathiafulvalene (TTF) derivative 1 substituted by two selenomethyl moieties are reported, with the aim to highlight the occurrence of chalcogen bonding interactions through activation of one of the two σ-holes on each Se atom, upon TTF oxidation into cation radical. Oxidation with iodine led to two different ionic phases incorporating 1+˙, with short and directional Se⋯I ChB interactions. In both salts, the 1+˙ radical cations are associated into diamagnetic dimers through a strong face-to-face, eclipsed, SOMO–SOMO interaction. Two different TCNQ salts were isolated, (i) a neutral charge-transfer complex with the weakly oxidizing TCNQMe2 and (ii) an ionic charge transfer salt with the stronger oxidant TCNQF2. In both co-crystals a Se⋯NC ChB bond is observed, in the prolongation of the CTTF–Se bond, with a notably stronger ChB within the ionic salt with TCNQF2, demonstrating the efficient charge activation of the ChB in these two closely related compounds, with alternated stacks of TTF and TCNQ derivatives.
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BibTeX
@article{bevan2026charge,
title = {{Charge activation of chalcogen bonding interactions in a bis(selenomethyl)-substituted tetrathiafulvalene and its salts}},
author = {Hugo Bevan and Yann Le Gal and Thierry Roisnel and Olivier Jeannin and Ie-Rang Jeon and Marc Fourmigué and Dominique Lorcy},
journal = {CrystEngComm},
year = {2026},
month = jul,
doi = {10.1039/d6ce00574h},
url = {https://hal.science/hal-05742466v1},
note = {CC BY-NC 4.0},
}
RIS
TY - JOUR
TI - Charge activation of chalcogen bonding interactions in a bis(selenomethyl)-substituted tetrathiafulvalene and its salts
AU - Hugo Bevan
AU - Yann Le Gal
AU - Thierry Roisnel
AU - Olivier Jeannin
AU - Ie-Rang Jeon
AU - Marc Fourmigué
AU - Dominique Lorcy
PY - 2026
DA - 2026/07/15
JO - CrystEngComm
DO - 10.1039/d6ce00574h
UR - https://hal.science/hal-05742466v1
AB - The preparation, crystal structure and electrochemical properties of a novel tetrathiafulvalene (TTF) derivative 1 substituted by two selenomethyl moieties are reported, with the aim to highlight the occurrence of chalcogen bonding interactions through activation of one of the two σ-holes on each Se atom, upon TTF oxidation into cation radical. Oxidation with iodine led to two different ionic phases incorporating 1+˙, with short and directional Se⋯I ChB interactions. In both salts, the 1+˙ radical cations are associated into diamagnetic dimers through a strong face-to-face, eclipsed, SOMO–SOMO interaction. Two different TCNQ salts were isolated, (i) a neutral charge-transfer complex with the weakly oxidizing TCNQMe2 and (ii) an ionic charge transfer salt with the stronger oxidant TCNQF2. In both co-crystals a Se⋯NC ChB bond is observed, in the prolongation of the CTTF–Se bond, with a notably stronger ChB within the ionic salt with TCNQF2, demonstrating the efficient charge activation of the ChB in these two closely related compounds, with alternated stacks of TTF and TCNQ derivatives.
SN - 1466-8033
ER -