Erratum: London Dispersion-Assisted Low-Temperature Gas Phase Synthesis of Hydrogen Bond-Inserted Complexes

Lange, Manuel; Sennert, Elisabeth; Suhm, Martin A.

doi:10.1055/s-0042-1752671

Cited by 2 publications

(9 citation statements)

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“…Replacement of the tert -butyl group by a halogen (Cl, Br) also blocks insertion more or less completely but now insertion is thermoneutral or uphill (Figure ), so this is more expected. A comparison of DFT predictions to CCSD(T) energies indicates some small but systematic errors in the former, also based on experimental findings . As Figure suggests for the glycolate case, a shift in computed relative energies on the order of a few kJ mol –1 may already explain the experimental preferences without having to invoke blocking barriers.…”

Section: Representative System Classesmentioning

confidence: 66%

“…This is also due to the dispersion interaction of the phenyl ring with the hydroxyester, which raises the barrier for interconversion. By adding a tert -butyl group in the para position, the barrier is further increased and now the insertion is already incomplete for methyl glycolate . Replacement of the tert -butyl group by a halogen (Cl, Br) also blocks insertion more or less completely but now insertion is thermoneutral or uphill (Figure ), so this is more expected.…”

Section: Representative System Classesmentioning

confidence: 99%

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Dispersion Control over Molecule Cohesion: Exploiting and Dissecting the Tipping Power of Aromatic Rings

Mata,

Zhanabekova,

Obenchain

et al. 2024

Acc. Chem. Res.

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Metrics & MoreArticle Recommendations * sı Supporting Information CONSPECTUS:We have learned over the past years how London dispersion forces can be effectively used to influence or even qualitatively tip the structure of aggregates and the conformation of single molecules. This happens despite the fact that single dispersion contacts are much weaker than competing polar forces. It is a classical case of strength by numbers, with the importance of London dispersion forces scaling with the system size. Knowledge about the tipping points, however difficult to attain, is necessary for a rational design of intermolecular forces. One requires a careful assessment of the competing interactions, either by sensitive spectroscopic techniques for the study of the isolated molecules and aggregates or by theoretical approaches. Of particular interest are the systems close to the tipping point, when dispersion interactions barely outweigh or approach the strength of the other interactions. Such subtle cases are important milestones for a scale-up to realistic multi-interaction situations encountered in the fields of life and materials science. In searching for examples that provide ideal competing interactions in complexes and small clusters, aromatic systems can offer a diverse set of molecules with a variation of dispersion and electrostatic forces that control the dominant and peripheral interactions. Our combined spectroscopic and theoretical investigations provide valuable insights into the balance of intermolecular forces because they typically allow us to switch the aromatic substituent on and off. High-resolution rotational spectroscopy serves as a benchmark for molecular structures, as correct calculations should be based on correct geometries. When discussing the competition with other noncovalent interactions, obvious competitors are directional hydrogen bonds. As a second counterweight to aryl interactions, we will discuss aurophilic/ metallophilic interactions, which also have a strong stabilization with a small number of atoms involved. Vibrational spectroscopy is most sensitive to interactions of light atoms, and the competition of OH hydrogen bonds with dispersion forces in a molecular aggregate can be judged well by the OH stretching frequency. Experiments in the gas phase are ideal for gauging the accuracy of quantum chemical predictions free of solvent forces. A tight collaboration utilizing these three methods allows experiment vs experiment vs theory benchmarking of the overall influence of dispersion in molecular structures and energetics.

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Section: Representative System Classesmentioning

confidence: 66%

Section: Representative System Classesmentioning

confidence: 99%

Dispersion Control over Molecule Cohesion: Exploiting and Dissecting the Tipping Power of Aromatic Rings

Mata,

Zhanabekova,

Obenchain

et al. 2024

Acc. Chem. Res.

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“…Because the driving force of hydrogen bond isomerisation is weak and the barrier rather broad, it is difficult to say whether a subtle energy penalty will result in substantial depopulation by simple carrier gas collisions or more elaborate mechanisms. 16,74,75…”

Section: Assessment Of Experimental Uncertainty Sourcesmentioning

confidence: 99%

“…The energy freed upon complexation is in principle enough to induce thermal isomerisation even in a supersonic jet expansion. 16,74,75 Such processes are still poorly understood, unlike corresponding laser-induced processes. 76,77 Therefore, partial relaxation of t2NA O to the further solvent-stabilised c2NA O should not be strictly ruled out but is unlikely to be quantitative.…”

Section: Energiesmentioning

confidence: 99%

“…One is the ground state preference for one over other structural arrangements of the complex in the competition of intermolecular forces. It is addressed by the concept of intermolecular energy balances, [14][15][16] where systems are picked for being ambivalent in terms of two different arrangements of their constituents. [17][18][19][20][21][22][23][24] The other aspect is the influence of molecular excitation of the components on this structural arrangement of the complex, due to the coupling of intramolecular degrees of freedom with intermolecular ones.…”

Section: Introductionmentioning

confidence: 99%

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Subtle hydrogen bond preference and dual Franck–Condon activity – the interesting pairing of 2-naphthol with anisole

Nejad

Pérez‐Mellor

Lange

et al. 2023

Phys. Chem. Chem. Phys.

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Erratum: London Dispersion-Assisted Low-Temperature Gas Phase Synthesis of Hydrogen Bond-Inserted Complexes

Cited by 2 publications

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Dispersion Control over Molecule Cohesion: Exploiting and Dissecting the Tipping Power of Aromatic Rings

Dispersion Control over Molecule Cohesion: Exploiting and Dissecting the Tipping Power of Aromatic Rings

Subtle hydrogen bond preference and dual Franck–Condon activity – the interesting pairing of 2-naphthol with anisole

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