Stability of doubly and triply H-bonded complexes governed by acidity–basicity relationships

Narváez, Wilmer E. Vallejo; Jiménez, Eddy I.; Cantú-Reyes, Margarita; Yatsimirsky, Anatoly K.; Hernández‐Rodríguez, Marcos; Rocha‐Rinza, Tomás

doi:10.1039/c8cc06967k

Cited by 13 publications

(10 citation statements)

References 22 publications

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“…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.…”

Section: Energy Components In Hydrogen Bondssupporting

confidence: 75%

“…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.…”

Section: Secondary Electrostatic Interactionsmentioning

confidence: 99%

“…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.…”

Section: Secondary Electrostatic Interactionsmentioning

confidence: 99%

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

Lubbe

Guerra

2019

Chemistry An Asian Journal

148

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Hydrogen bonds are a complex interplay between different energy components, and their nature is still subject of an ongoing debate. In this minireview, we therefore provide an overview of the different perspectives on hydrogen bonding. This will be done by discussing the following individual energy components: 1) electrostatic interactions, 2) charge‐transfer interactions, 3) π‐resonance assistance, 4) steric repulsion, 5) cooperative effects, 6) dispersion interactions and 7) secondary electrostatic interactions. We demonstrate how these energetic factors are essential in a correct description of the hydrogen bond, and discuss several examples of systems whose energetic and geometrical features are not captured by easy‐to‐use predictive models.

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Section: Energy Components In Hydrogen Bondssupporting

confidence: 75%

Section: Secondary Electrostatic Interactionsmentioning

confidence: 99%

Section: Secondary Electrostatic Interactionsmentioning

confidence: 99%

See 1 more Smart Citation

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

Lubbe

Guerra

2019

Chemistry An Asian Journal

148

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“…Nowadays, the SEI model is teaching material in organic chemistry textbooks , and is widely used in supramolecular chemistry to predict and explain the relative strengths of self-assembled systems. − However, the validity of the model has been questioned, and the predicted trends in hydrogen bond stabilities are not always in line with experimental trends. − Popelier and Joubert, Tiwari and Vanka, and most recently Hernández-Rodrı́guez, Rocha-Rinza, and co-workers , have demonstrated that all possible atom–atom interactions should be considered, not just the interactions between the frontier atoms as is done in the SEI model. Clark, Murray, and Politzer state that hydrogen bonds can be described in terms of Coulombic interactions, but only when the exact electronic density (or a reasonable approximation) is known and the polarization of each molecule is taken into account. , …”

Section: Introductionmentioning

confidence: 99%

Secondary Electrostatic Interaction Model Revised: Prediction Comes Mainly from Measuring Charge Accumulation in Hydrogen-Bonded Monomers

et al. 2019

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The secondary electrostatic interaction (SEI) model is often used to predict and explain relative hydrogen bond strengths of self-assembled systems. The SEI model oversimplifies the hydrogen-bonding mechanisms by viewing them as interacting point charges, but nevertheless experimental binding strengths are often in line with the model’s predictions. To understand how this rudimentary model can be predictive, we computationally studied two tautomeric quadruple hydrogen-bonded systems, DDAA-AADD and DADA-ADAD. Our results reveal that when the proton donors D (which are electron-donating) and the proton acceptors A (which are electron-withdrawing) are grouped together as in DDAA, there is a larger accumulation of charge around the frontier atoms than when the proton donor and acceptor groups are alternating as in DADA. This accumulation of charge makes the proton donors more positive and the proton acceptors more negative, which enhances both the electrostatic and covalent interactions in the DDAA dimer. The SEI model is thus predictive because it provides a measure for the charge accumulation in hydrogen-bonded monomers. Our findings can be understood from simple physical organic chemistry principles and provide supramolecular chemists with meaningful understanding for tuning hydrogen bond strengths and thus for controlling the properties of self-assembled systems.

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“… 41 Rocha-Rinza and co-workers showed that the hydrogen bond strength is enhanced with increased acidity and basicity of the hydrogen bond donor and acceptor groups, respectively. 45 , 46 …”

Section: Introductionmentioning

confidence: 99%

Tuning the Binding Strength of Even and Uneven Hydrogen-Bonded Arrays with Remote Substituents

et al. 2020

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We investigated the tunability of hydrogen bond strength by altering the charge accumulation around the frontier atoms with remote substituents. For pyridine···H 2 O with NH 2 and CN substituted at different positions on pyridine, we find that the electron-withdrawing CN group decreases the negative charge accumulation around the frontier atom N, resulting in weakening of the hydrogen bond, whereas the electron-donating NH 2 group increases the charge accumulation around N, resulting in strengthening of the hydrogen bond. By applying these design principles on DDAA–AADD, DADA–ADAD, DAA–ADD, and ADA–DAD hydrogen-bonded dimers, we find that the effect of the substituent is delocalized over the whole molecular system. As a consequence, systems with an equal number of hydrogen bond donor (D) and acceptor (A) atoms are not tunable in a predictable way because of cancellation of counteracting strengthening and weakening effects. Furthermore, we show that the position of the substituent and long-range electrostatics can play an important role as well. Overall, the design principles presented in this work are suitable for monomers with an unequal number of donor and acceptor atoms and can be exploited to tune the binding strength of supramolecular building blocks.

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Stability of doubly and triply H-bonded complexes governed by acidity–basicity relationships

Abstract: The acidity–basicity interplay model allows explaining and tuning the relative stability of doubly and triply H-bonded complexes.

Cited by 13 publications

References 22 publications

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

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

Secondary Electrostatic Interaction Model Revised: Prediction Comes Mainly from Measuring Charge Accumulation in Hydrogen-Bonded Monomers

Tuning the Binding Strength of Even and Uneven Hydrogen-Bonded Arrays with Remote Substituents

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