From Charge‐Transfer Adducts to (Tri)Halide‐Templated Supramolecular Cages: Covalent vs Ionic Products in the Reactions of Pyridin‐4‐ylthio‐Substituted Tetrathiafulvalene With Dihalogens and Interhalogens
- 1Dipartimento Di Scienze Chimiche e Geologiche Università Degli Studi di Cagliari Cagliari Italy
- 2Université De Strasbourg, CNRS, CMC UMR 7140 Strasbourg France
- 3Centro Servizi di Ateneo per La Ricerca (CeSAR) Università Degli Studi di Cagliari Cagliari Italy
Abstract
The reactivity of tetra(pyridin‐4‐ylthio)tetrathiafulvalene ( L 1 ) toward dihalogens (Br 2 , I 2 )/interhalogens (ICl, IBr) was investigated by crystallographic, microanalytical, spectroscopic, and hybrid‐DFT approaches. A divergence in reactivity was observed depending on the halogen reagent. The reactions of L 1 with I 2 yielded a 1:4 adduct L 1 ·4I 2 ( 1 ), featuring four independent N···I─I interactions within a single polytopic scaffold. Reactions of L 1 with Br 2 , ICl, and IBr afforded ionic species ( 2–6 ), containing the protonated donor counterbalanced by discrete tri(inter)halide anions such as [Br 3 ] − , [ICl 2 ] − , and [IBr 2 ] − . These compounds showed diverse supramolecular cage‐like architectures, often involving hydrogen‐bonded networks. [H 4 L 1 ]( L 1 )[IBr 2 ] 4 ·2CH 3 CN·2.4CHCl 3 ( 4 ) contains a tetracationic capsule [(H 4 L 1 )( L 1 )] 4+ stabilized by N–H···N HBs and templated at a [IBr 2 ] − guest. Both the N···I─I fragment in compound 1 and the tri(inter)halides in compounds 2–6 follow a common structural correlation between the normalized bond elongations typical of three‐body systems. Hybrid‐DFT QTAIM, NBO, Hirshfeld, and Bader charges, along with NCI index calculations allowed to quantify the CT interactions and the extent of ionic/covalent contributions to the HaBs in compound 1 , analysis of the anion–cation interactions in the inclusion complex [(H 4 L 1 )( L 1 )(IBr 2 )] 3+ , and reproduction of the observed structural trends, highlighting the continuous nature of covalent‐to‐electrostatic interactions in apparently different three‐body systems.
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BibTeX
@article{caria2026from,
title = {{From Charge‐Transfer Adducts to (Tri)Halide‐Templated Supramolecular Cages: Covalent vs Ionic Products in the Reactions of Pyridin‐4‐ylthio‐Substituted Tetrathiafulvalene With Dihalogens and Interhalogens}},
author = {Anna Caria and Stéphane A. Baudron and M. Carla Aragoni and Vito Lippolis and Anna Pintus and Enrico Podda and Massimiliano Arca},
journal = {Chemistry - A European Journal},
year = {2026},
month = aug,
doi = {10.1002/chem.71483},
url = {https://hal.science/hal-05853515v1},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - From Charge‐Transfer Adducts to (Tri)Halide‐Templated Supramolecular Cages: Covalent vs Ionic Products in the Reactions of Pyridin‐4‐ylthio‐Substituted Tetrathiafulvalene With Dihalogens and Interhalogens
AU - Anna Caria
AU - Stéphane A. Baudron
AU - M. Carla Aragoni
AU - Vito Lippolis
AU - Anna Pintus
AU - Enrico Podda
AU - Massimiliano Arca
PY - 2026
DA - 2026/08/05
JO - Chemistry - A European Journal
DO - 10.1002/chem.71483
UR - https://hal.science/hal-05853515v1
AB - The reactivity of tetra(pyridin‐4‐ylthio)tetrathiafulvalene ( L 1 ) toward dihalogens (Br 2 , I 2 )/interhalogens (ICl, IBr) was investigated by crystallographic, microanalytical, spectroscopic, and hybrid‐DFT approaches. A divergence in reactivity was observed depending on the halogen reagent. The reactions of L 1 with I 2 yielded a 1:4 adduct L 1 ·4I 2 ( 1 ), featuring four independent N···I─I interactions within a single polytopic scaffold. Reactions of L 1 with Br 2 , ICl, and IBr afforded ionic species ( 2–6 ), containing the protonated donor counterbalanced by discrete tri(inter)halide anions such as [Br 3 ] − , [ICl 2 ] − , and [IBr 2 ] − . These compounds showed diverse supramolecular cage‐like architectures, often involving hydrogen‐bonded networks. [H 4 L 1 ]( L 1 )[IBr 2 ] 4 ·2CH 3 CN·2.4CHCl 3 ( 4 ) contains a tetracationic capsule [(H 4 L 1 )( L 1 )] 4+ stabilized by N–H···N HBs and templated at a [IBr 2 ] − guest. Both the N···I─I fragment in compound 1 and the tri(inter)halides in compounds 2–6 follow a common structural correlation between the normalized bond elongations typical of three‐body systems. Hybrid‐DFT QTAIM, NBO, Hirshfeld, and Bader charges, along with NCI index calculations allowed to quantify the CT interactions and the extent of ionic/covalent contributions to the HaBs in compound 1 , analysis of the anion–cation interactions in the inclusion complex [(H 4 L 1 )( L 1 )(IBr 2 )] 3+ , and reproduction of the observed structural trends, highlighting the continuous nature of covalent‐to‐electrostatic interactions in apparently different three‐body systems.
SN - 0947-6539
SN - 1521-3765
ER -