{
  "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.",
  "abstract_shown": true,
  "affiliations": [
    "Dipartimento Di Scienze Chimiche e Geologiche Università Degli Studi di Cagliari Cagliari Italy",
    "Université De Strasbourg, CNRS, CMC UMR 7140 Strasbourg France",
    "Centro Servizi di Ateneo per La Ricerca (CeSAR) Università Degli Studi di Cagliari Cagliari Italy"
  ],
  "article_type": "research article",
  "arxiv": null,
  "author_total": 7,
  "authors": [
    {
      "affs": [
        0
      ],
      "name": "Anna Caria",
      "orcid": "0009-0001-1530-7326"
    },
    {
      "affs": [
        1
      ],
      "name": "Stéphane A. Baudron",
      "orcid": "0000-0002-1517-704X"
    },
    {
      "affs": [
        0
      ],
      "name": "M. Carla Aragoni",
      "orcid": "0000-0002-5010-7370"
    },
    {
      "affs": [
        0,
        2
      ],
      "name": "Vito Lippolis",
      "orcid": "0000-0001-8093-576X"
    },
    {
      "affs": [
        0
      ],
      "name": "Anna Pintus",
      "orcid": "0000-0001-6069-9771"
    },
    {
      "affs": [
        0,
        2
      ],
      "name": "Enrico Podda",
      "orcid": "0000-0002-4329-7751"
    },
    {
      "affs": [
        0
      ],
      "name": "Massimiliano Arca",
      "orcid": "0000-0002-0058-6406"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/brr5ss5eg28h4.bib",
  "cited_by": 0,
  "doi": "10.1002/chem.71483",
  "fulltext_url": "https://pmc.ncbi.nlm.nih.gov/articles/PMC13730010/",
  "id": "brr5ss5eg28h4",
  "issns": [
    "0947-6539",
    "1521-3765"
  ],
  "landing_url": "https://hal.science/hal-05853515v1",
  "language": "en",
  "licence": "CC-BY-4.0",
  "licence_label": "CC BY 4.0",
  "licence_source": "article",
  "licence_url": "https://creativecommons.org/licenses/by/4.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "hal",
      "0.chim"
    ],
    [
      "heading",
      "Research Article"
    ],
    [
      "openalex",
      "1606|Crystallography and molecular interactions"
    ]
  ],
  "openalex": "W7172512511",
  "pdf_url": "https://hal.science/hal-05853515/document",
  "pmcid": "PMC13730010",
  "pmid": "42555157",
  "published": "2026-08-05",
  "publisher": "Wiley-VCH Verlag",
  "ris": "https://research.draconitic.com/paper/brr5ss5eg28h4.ris",
  "sources": [
    {
      "first_seen": "2026-11-06T12:20:44Z",
      "native_id": "hal-05853515",
      "source": "hal",
      "url": "https://hal.science/hal-05853515v1"
    },
    {
      "first_seen": "2026-11-07T12:22:41Z",
      "native_id": "PMC13730010",
      "source": "pmc",
      "url": "https://doi.org/10.1002/chem.71483"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1606|Crystallography and molecular interactions",
      "subfield": "physical"
    }
  ],
  "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",
  "title_text": "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",
  "type": "peer-reviewed",
  "updated_at": "2026-11-07T12:22:41Z",
  "url": "https://research.draconitic.com/paper/brr5ss5eg28h4",
  "venue": "Chemistry - A European Journal",
  "versions": []
}