Acid-Base theories/definitions were elaborated far before the onset of Supramolecular Chemistry. While acid-base official definitions have long remained untouched, in the last decade Supramolecular Chemistry provided many new additions to the IUPAC chemical vocabulary, e.g. halogen-, chalcogen-, pnictogen-bonds. The discussion moves from two distinct-yet-connected premises. First, the scope of supramolecular chemistry is addressed, and it is showed how existing official acid-base frameworks, in principle subtending to all donor-acceptor interactions – non-covalent ones included – are found restrictive with respect to the general consensus and understanding of supramolecular interactions. Second, attention is brought to some underappreciated elements of novelty in the halogen- and post-halogen-bond IUPAC definitions, which, again, are not mirrored in current acid-base definitions. For these reasons, a quest is herein undertaken for an acid-base framework fully apt for supramolecular chemistry. This requires: first, reconsideration of both classical acid-base theories, including non-canonical ones (Lewis, Brønsted-Lowry, Arrhenius, Lux-Flood, SST, Usanovich, ionotropic definitions, etc…); second, re-evaluation of modern notable post-Lewis restatements (Mulliken, Jensen, Huheey, Drago, etc…). Discussion also addresses opportunities and reasons for these statements never to have reached IUPAC formalization. In such literature inspection, briefly addressing some History of Chemistry and Philosophy of Science topics, insights and key elements are collected which could assist in the formalization of an acid-base framework geared towards supramolecular chemistry. Brief discussion of the desirability and potential benefits of such an operation are discussed in a persistent dialogue among old ideas and modern supramolecular advancements. The ultimate goal of this work is to reconnect the acid-base historical discourse with its supramolecular modern declination, advocating for a holistic and inclusive view that, hopefully, could be one day officially formalized.

The acid-base concept in modern supramolecular chemistry

Savastano, Matteo
2026-01-01

Abstract

Acid-Base theories/definitions were elaborated far before the onset of Supramolecular Chemistry. While acid-base official definitions have long remained untouched, in the last decade Supramolecular Chemistry provided many new additions to the IUPAC chemical vocabulary, e.g. halogen-, chalcogen-, pnictogen-bonds. The discussion moves from two distinct-yet-connected premises. First, the scope of supramolecular chemistry is addressed, and it is showed how existing official acid-base frameworks, in principle subtending to all donor-acceptor interactions – non-covalent ones included – are found restrictive with respect to the general consensus and understanding of supramolecular interactions. Second, attention is brought to some underappreciated elements of novelty in the halogen- and post-halogen-bond IUPAC definitions, which, again, are not mirrored in current acid-base definitions. For these reasons, a quest is herein undertaken for an acid-base framework fully apt for supramolecular chemistry. This requires: first, reconsideration of both classical acid-base theories, including non-canonical ones (Lewis, Brønsted-Lowry, Arrhenius, Lux-Flood, SST, Usanovich, ionotropic definitions, etc…); second, re-evaluation of modern notable post-Lewis restatements (Mulliken, Jensen, Huheey, Drago, etc…). Discussion also addresses opportunities and reasons for these statements never to have reached IUPAC formalization. In such literature inspection, briefly addressing some History of Chemistry and Philosophy of Science topics, insights and key elements are collected which could assist in the formalization of an acid-base framework geared towards supramolecular chemistry. Brief discussion of the desirability and potential benefits of such an operation are discussed in a persistent dialogue among old ideas and modern supramolecular advancements. The ultimate goal of this work is to reconnect the acid-base historical discourse with its supramolecular modern declination, advocating for a holistic and inclusive view that, hopefully, could be one day officially formalized.
2026
Brønsted Acids and Bases
Donor-Acceptor interactions
Halogen Bond
Lewis Acids and Bases
Non-covalent Interactions
Nucleophiles and Electrophiles
Supramolecular Chemistry
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/20.500.12078/31008
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