Fluoride‐Selective Host Based on Anion–π Interactions, Ion Pairing, and Hydrogen Bonding: Synthesis and Fluoride‐Ion Sandwich Complex

Abstract

A fluoride sandwich: A cylindrophane macrocycle framed with cyanuric acid rings selectively complexes fluoride ion by a combination of anion–π interactions and ion‐pair‐reinforced hydrogen bonds. This compound is the first example of a purpose‐designed host that exploits anion–π bonding.

Tuning of the anion–π interaction

“…For two complexes, where the BSSE energies are large (18 and 19), we have carried out BSSE-corrected geometry optimizations, and we have obtained comparable results, very similar interaction energies and slightly larger equilibrium distances. For complexes where the nitrogen atoms of s-triazine are forming covalent bonds with silver and boron (20)(21)(22)(23)(24)(25)(26)(27)(28), the BSSE correction has not been applied. Some interesting points can be extracted from the geometrical results.…”

“…In addition, the favorable interaction of anions with p-acidic rings, namely anion-p interaction [19][20][21], has been extensively studied theoretically [22], and its importance has been corroborated by a great deal of experimental work. For instance, a new family of anion receptors based on anionp interactions has emerged [23][24][25][26][27][28][29][30][31][32]. Moreover, the design and synthesis of highly selective anion channels [33][34][35][36][37][38][39][40] Electronic supplementary material The online version of this article (doi:10.1007/s00214-012-1219-6) contains supplementary material, which is available to authorized users.…”

Interplay between anion‐π and hydrogen bonding interactions

“…1 Among them, anion-p interactions [2][3][4][5][6] have attracted considerable attention in the last 5 years. 7 There is a great deal of experimental [8][9][10][11][12][13] and theoretical [14][15][16][17] work that evidence that the anion-p interactions play a prominent role in several areas of chemistry, such as molecular recognition 18 and transmembrane anion transport. 19,20 Anion coordination is an important and challenging aspect of contemporary supramolecular chemistry.…”

Anion‐π‐Wechselwirkungen ins rechte Licht gerückt

“…Mascal und Mitarbeiter beschrieben kürzlich eine Anwendung von p-Anion-p-Sandwichbindungen bei der Konstruktion [139] und der Synthese [64] [140] aber dieser Rezeptor führt einen neuen Typ von Anionenbindung ein, bei dem Anion-p-Wechselwirkungen zusammen mit herkçmmlicher Ionenpaarung, Wasserstoffbrücken und dem klassischen "Vororganisationseffekt" wirken.…”

“…Struktur eines fluoridbindenden Cylindrophan-Makrocyclus und die Rçntgenkristallstruktur seines F À -Komplexes (KISDIA). [64,139] klärung der Anion-p-Wechselwirkung in den Cokristallen. Die Selbstorganisation der Anionen mit den p-Säuren ergab eine Reihe neuer eindimensionaler Strukturen aus parallelen Stapeln alternierender p-Säuren und Anionen.…”