Intermolecular n→π* Interactions in Supramolecular Chemistry and Catalysis

Abstract

The n→π* interactions describing attractive force between lone pairs (lps) of nucleophile and carbonyl groups have recently attracted growing attentions in various disciplines. So far, such non‐covalent driving force are mainly concentrated to intramolecular systems. Intermolecular n→π* interactions in principle could produce fascinated supramolecular systems or facilitate organic reactions, however, they remain largely underexplored due to the very weak energy of individual interaction. This review attempts to give an overview of the challenging intermolecular n→π* interactions, much efforts emphasize the supramolecular systems, catalytic processes and spectroscopic measurements

Dual reactivity based dynamic covalent chemistry: mechanisms and applications

“…108,109 Despite tracing back to Bürgi–Dunitz angle for nucleophilic addition of carbonyls 110 and contributing to structures of peptides/proteins, 111 n → π* interactions as an emerging type of supramolecular bonding forces have been capturing increasing attention recently. 112 The n → π* interaction from donor X (NMe 2 , OMe, SMe, F, Cl, Br, I) to acceptor aldehyde/imine within 2-X-2′-formylbiphenyl ( 26 and 27 ) was supported through a collection of experimental and computational evidence (Fig. 10b).…”

Neighboring Effects of Sulfur Oxidation State on Dynamic Covalent Bonds and Assemblies

“…In order to gauge the thermodynamic effect on imine DCC, a series of aldehyde competition experiments were carried out (Figures S37–S41 and Table S4). As we have shown with n → π* interactions and chalcogen bonding, changes in dynamic covalent exchange equilibria can be used for the quantification of the intercorrelation between noncovalent interactions and DCRs . When a mixture of 1a , 1b , and 1-butylamine (1.0 equiv) was tracked, the equilibrium was reached after 50 days (exchange 1, Figure A).…”

Discovering trends in the Lewis acidity of beryllium and magnesium hydrides and fluorides with increasing clusters size

“…Noncovalent interactions (NCIs), despite being generally rather weak, dictate the properties of many molecular systems and their response to environmental perturbations, playing a fundamental role in chemistry, biology and materials science. Not surprisingly, they receive increasing attention in many different fields, such as supramolecular chemistry and catalysis, 1–3 new functional materials, 4 polymers, 5 surface phenomena, 6–8 molecular sensors, 9,10 or biochemistry, 11–15 just to cite a few of the most recent contributions in different areas. Although we are still far from having a complete understanding of these phenomena, because the description of these weak interactions is a real challenge, 16 the efforts to establish their intimate nature continue at present.…”