Acidity and basicity interplay in amide and imide self-association

Abstract

Simple acid–base properties explain the differences in amide and imide dimerisation, and represent an alternative to the secondary interactions hypothesis.

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

“…In line with these results are the recent findings by Hernández‐Rodríguez, Rocha‐Rinza and co‐workers, who developed the acidity‐basicity interplay (ABI) model to explain the difference in association constants . In this model, the HB strength increases with the acidity of the proton donor and basicity of the proton acceptor groups.…”

“…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.…”

“…In line with these resultsa re the recent findings by Hernµndez-Rodríguez, Rocha-Rinza and co-workers, who developed the acidity-basicity interplay (ABI) model to explain the difference in associationc onstants. [82,83] In this model,t he HB strength increases with the acidity of the proton donora nd basicity of the proton acceptor groups. The ABI modelw as not only capable to explain the order of stability or triply Hbondeds ystems (AAA-DDD > AAD-DDA > ADA-DAD), but also the relative order of dimers with the same HB pattern.…”

“…The HB mechanism is ac omplex interplay between different energy terms, whose importance depend on the molecular system.I nt his review, we have seen severale xamples of systems whose energetic features are not capturedb yeasy-to-use predictivem odels, including the relative stability of the mismatched DNA base pairs GG and CC (entirely governed by the difference in steric repulsion), [74] the energetic trends in (XOH) 2 with X = Hu pt otBu (entirely determined by dispersion interactions), [76] the HB strength in oligomer chains in whicht he HB strength depends on both the length of and the positioni n the chain (resultingf rom cooperative effects) [62,69] and the significant atom-atomp airwise interactions that are not considered by the SEI model. [26,81,83] This emphasizes the importance of using quantum-chemical calculations such as density functional theory (DFT) or post-Hartree-Fock methodsf or ac orrect description of the HB. As our understanding of the HB mechanism is improving,w ee xpect that the rational tuningo fi ndividuale nergy components will start to play am ore important role in the artificial design of self-assembled systems.…”

Interacting Quantum Atoms—A Review

“…Vallejo Narváez et al used IQA to rationalise that amides dimerise more strongly than imides in spite of their lower acidity [ 134 ]. They found that the traditional Jorgensen Secondary Interactions Hypothesis (of repulsion between carbonyl oxygens) fails once the carbon atoms are included in the calculations.…”