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Nitrogen\u2010containing tellurium compounds are well\u2010suited for this purpose, as they form a variety of solid\u2010state structures through ChBs. Despite prior studies addressing substituent effects in benzotellurazoles, the influence of fluorine atoms on the benzene backbone of 1,3\u2010benzotellurazoles remains to be investigated in the context of solid\u2010state arrangement. Here, we demonstrate that the incorporation of fluorine atoms can impact the nature and quantity of ChBs in the solid state. The electron\u2010withdrawing properties of the introduced substituents result in alterations to the ChB donor (Te) and acceptor (N) properties, leading to a preferential interaction with competing Lewis bases such as carbonyl groups. A noteworthy exception was noticed for the derivatives with a nitrile group at position 2. Regardless of the number of fluorine atoms, a high degree of 3D cross\u2010linking can be observed via a 5\u2010ChBs\u20105\u2010neighbors motif, including a characteristic two\u2010lone\u2010pair\/one\u2010\u03c3\u2010hole interaction. These findings offer valuable design principles for supramolecular materials, particularly in the context of crystal engineering.<\/jats:p>","DOI":"10.1002\/chem.202502731","type":"journal-article","created":{"date-parts":[[2025,10,22]],"date-time":"2025-10-22T04:58:06Z","timestamp":1761109086000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["Supramolecular 3D Polymers Created via Chalcogen Bonding Using Benzotellurazoles as Planar Recognition Units"],"prefix":"10.1002","volume":"31","author":[{"given":"Jan","family":"Schulte","sequence":"first","affiliation":[{"name":"Fakult\u00e4t f\u00fcr Chemie Universit\u00e4t Duisburg\u2010Essen, Universit\u00e4tsstr. 7  Essen D\u201045117 Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Saber","family":"Mehrparvar","sequence":"additional","affiliation":[{"name":"Fakult\u00e4t f\u00fcr Chemie Universit\u00e4t Duisburg\u2010Essen, 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