Exploiting directional long range secondary forces for regulating electrostatics-dominated noncovalent interactions

Abstract

It has been well established that long range secondary electrostatic interactions (SEIs) have a significant effect on the stability of supramolecular complexes.

Acidity and basicity interplay in amide and imide self-association

“…Finally, the results of our investigation suggest a different approach for the analysis of the stability of multiple hydrogen-bonded systems such as uracil–diamino purine, cytosine–guanine and ADA–DAD systems. 58 , 59 Generally, these systems are examined by considering only the acidity and basicity of the intermediate hydrogen bond and the JSIH. It would be nevertheless desirable to examine the Brønsted–Lowry acid/base properties for every HB in the system which could lead to valuable insights about the molecular recognition of hydrogen-bonded homo- and heterodimers.…”

Hydrogen bond design principles

“…Especially robust multipoint hydrogen bonding arrays have been prepared following the SEI model ( Figure 10). 67,68 Statistical analyses supporting the SEI model have shown that the association strengths of hydrogen bonded arrays could be reproduced by summing up empirical increments 69,70 or by combining calculated electrostatic forces 71 that take into account the primary and secondary electrostatic interactions in complexes. It was suggested that F I G U R E 8 Examples of other diamine-based proton sponges: TMGN, P 2 -TPPN, t-Bu-P 2 , vinamidine, and a fluorene-based proton sponge electrostatic interactions between remote atom pairs in a hydrogen-bonded complex also could affect array association.…”

The Nature of Hydrogen Bonds: A Delineation of the Role of Different Energy Components on Hydrogen Bond Strengths and Lengths

“…They demonstrated that the SEI model ignores many significant (longrange) interactions, which led them to conclude that primary and secondary interactions constitute "a rather arbitrary subset".T he importance of considering additional atom-atom pairwise interactions has been confirmedb yo ther groups. [25,[81][82][83] Lukina nd Leszczynski [84] studied seventeen multiply H-bonded complexes to test the applicabilityo ft he SEI model,a nd concluded that "the stability information of a single complexc ould not be directly used to obtain stability data for H-bonded assemblies in general." Wu et al [84] showed with 26 triply and 20 quadruply H-bonded systemst hat the predictionsmade by the SEI model do not alwaysh old.…”

“…However, there are also cases in which this dipole‐dipole interpretation fails to explain the geometrical and energetic trends, such as the nonlinearity of the HF dimer or the large energetic differences between dimers with similar dipole moments . More recently, Tiwari and Vanka proposed to use the electrostatic force (which has directionality) rather than the electrostatic interaction for the description of noncovalent interactions. Good correlations were found between the electrostatic forces and the binding energy for a wide range of systems, including 28 base pairs that were studied in ref.…”