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Open AccessArticle

Stabilization of Supramolecular Networks of Polyiodides with Protonated Small Tetra-azacyclophanes

1
Department of Chemistry “Ugo Schiff”, University of Florence, Via della Lastruccia 3, 50019 Sesto Fiorentino, Italy
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ICMol, Department of Inorganic Chemistry, University of Valencia, C/Catedrático José Beltrán 2, 46980 Paterna, Spain
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Departamento de Química Orgánica, Universidad de Valencia, C/Dr. Moliner s/n, 46100 Burjassot, Valencia, Spain
*
Authors to whom correspondence should be addressed.
Inorganics 2019, 7(4), 48; https://doi.org/10.3390/inorganics7040048
Received: 1 March 2019 / Revised: 21 March 2019 / Accepted: 26 March 2019 / Published: 1 April 2019
(This article belongs to the Special Issue Novel Non-Covalent Interactions)
Polyiodide chemistry is among the first historically reported examples of supramolecular forces at work. To date, owing to the increasingly recognized role of halogen bonding and the incorporation of iodine-based components in several devices, it remains an active field of theoretical and applied research. Herein we re-examine azacyclophanes as a class of ligands for the stabilization of iodine-dense three-dimensional networks, showing how we devised novel possible strategies starting from literature material. The new set of azacyclophane ligands affords novel crystal structures possessing intriguing properties, which develop on a double layer. At a macroscopic level, the obtained networks possess a very high iodine packing density (less than 2 times more diluted than crystalline I2): a simple parameter, IN, is also introduced to quickly measure and compare iodine packing density in different crystals. On the microscopic level, the present study provides evidence about the ability of one of the ligands to act as a three-dimensional supramolecular mold for the template synthesis of the rarely observed heptaiodide (I7) anion. Therefore, we believe our approach and strategy might be relevant for crystal engineering purposes. View Full-Text
Keywords: iodine; polyiodides; azacyclophanes; heptaiodide; supramolecular forces; iodine networks; anion coordination chemistry iodine; polyiodides; azacyclophanes; heptaiodide; supramolecular forces; iodine networks; anion coordination chemistry
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Savastano, M.; Martínez-Camarena, Á.; Bazzicalupi, C.; Delgado-Pinar, E.; Llinares, J.M.; Mariani, P.; Verdejo, B.; García-España, E.; Bianchi, A. Stabilization of Supramolecular Networks of Polyiodides with Protonated Small Tetra-azacyclophanes. Inorganics 2019, 7, 48.

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