Experimental Binding Energies in Supramolecular Complexes

Abstract

On the basis of many literature measurements, a critical overview is given on essential noncovalent interactions in synthetic supramolecular complexes, accompanied by analyses with selected proteins. The methods, which can be applied to derive binding increments for single noncovalent interactions, start with the evaluation of consistency and additivity with a sufficiently large number of different host-guest complexes by applying linear free energy relations. Other strategies involve the use of double mutant cycles, of molecular balances, of dynamic combinatorial libraries, and of crystal structures. Promises and limitations of these strategies are discussed. Most of the analyses stem from solution studies, but a few also from gas phase. The empirically derived interactions are then presented on the basis of selected complexes with respect to ion pairing, hydrogen bonding, electrostatic contributions, halogen bonding, π-π-stacking, dispersive forces, cation-π and anion-π interactions, and contributions from the hydrophobic effect. Cooperativity in host-guest complexes as well as in self-assembly, and entropy factors are briefly highlighted. Tables with typical values for single noncovalent free energies and polarity parameters are in the Supporting Information.

The Chaotropic Effect as an Assembly Motif in Chemistry

“…Accordingly, the unexpectedly high binding affinities of superchaotropic anions and the chaotropic effect as a generic driving force have recently found their entry into the important area of anion recognition 44, 65, 117, 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141, 142, 143…”

Parametrization of Non-covalent Interactions for Transition State Interrogation Applied to Asymmetric Catalysis

“…Although the determination and quantification of such interactions is highly desirable in order to predict, improve, and understand reaction performance, this is a difficult goal using purely empirical observations as NCIs are often low energy (0–2 kcal/mol) and dynamic. 1 In this vein, computational analysis of TSs can provide insight into significant influences in the selectivity-determining step(s). 2 However, as is always a consequence of TS interrogation, a detailed understanding of the roles of all reaction components is obligatory.…”

Partnering dispersion corrections with modern parameter-free double-hybrid density functionals

“…As a matter of fact, they influence the formation of biologically active compounds [1], the adsorption processes in layered materials [2][3][4], the drug delivery [5], or the supramolecular chemistry [6], to name just a few examples.…”