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

Nejad, Arman; Pérez‐Mellor, Ariel; Lange, Manuel; Alata, Ivan; Zehnacker‐Rentien, Anne; Suhm, Martin A.

doi:10.1039/d3cp00160a

Cited by 3 publications

(2 citation statements)

References 85 publications

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“…Other than for furan, the interconversion barrier is somewhat broader because it requires donor motion across the ring boundary. For both methanol 52 and 2-naphthol 53 as binding partners, theory is quite undecided about the docking preference, but in experiments, only the oxygen docking isomer is observed. 52 , 53 Considering the large change in donor character from methanol to 2-naphthol, this experimental uniformity, despite close competition, is again quite surprising.…”

Section: Representative System Classesmentioning

confidence: 99%

“…For both methanol 52 and 2-naphthol 53 as binding partners, theory is quite undecided about the docking preference, but in experiments, only the oxygen docking isomer is observed. 52 , 53 Considering the large change in donor character from methanol to 2-naphthol, this experimental uniformity, despite close competition, is again quite surprising. It is expected that relatively minor further modifications of the anisole can tip the balance in favor of π bonding.…”

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: 99%

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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Regularities and Anomalies in Neon Matrix Shifts of Hydrogen-Bonded O–H Stretching Fundamentals

Bödecker,

Mihrin,

Suhm

et al. 2024

J. Phys. Chem. A

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O−H bond stretching vibrations in hydrogen-bonded complexes embedded into cryogenic neon matrices are subtly downshifted from cold gas phase reference wavenumbers. To the extent that this shift is systematic, it enables neon matrices as more universally applicable spectroscopic benchmark environments for quantum chemical predictions. Outliers are indicative of either an assignment problem in one of the two cryogenic experiments or they reveal interesting dynamics or structural effects on the complexes as a function of the environment. We compile 6 literature-known pairs of experimental data in jet and neon matrix expansions and realize a 6-fold expansion of that number through targeted matrix isolation and/or slit jet expansion spectroscopy presented in this work. In many cases, the neon matrix shift is less than the uncertainty of the currently bestperforming blind quantum chemical predictions for the gas phase, but in specific cases, it may exceed the currently achievable theoretical accuracy. Some evidence for a positive correlation of the matrix shift with the hydrogen bond shift is found, similar to observations for helium nanodroplets. Outliers in particular for water acting as a donor are discussed, and in a few cases they call for a future reinvestigation. Substantial improvement in the correlation of the matrix shift with the hydrogen bond shift is achieved for ketone monohydrates by removing a vibrational resonance. New insights into nitrile hydration isomerism are obtained, and the linear OH stretching spectrum of the jet-cooled ammonia−water complex is presented for the first time. Vibrational spectroscopy in weakly perturbing solid rare gas quantum matrices for the benchmarking of gas phase theory and future explicit theoretical treatments of the quantum matrix environment to better understand the outliers are both encouraged.

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Anisole–Water and Anisole–Ammonia Complexes in Ground and Excited (S₁) States: A Multiconfigurational Symmetry-Adapted Perturbation Theory (SAPT) Study

Krzemińska,

Biczysko,

Pernal

et al. 2024

J. Phys. Chem. A

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Binary complexes of anisole have long been considered paradigm systems for studying microsolvation in both the ground and electronically excited states. We report a symmetry-adapted perturbation theory (SAPT) analysis of intermolecular interactions in anisole–water and anisole–ammonia complexes within the framework of the multireference SAPT(CAS) method. Upon the S1 ← S0 electronic transition, the hydrogen bond in the anisole–water dimer is weakened, which SAPT(CAS) shows to be determined by changes in the electrostatic energy. As a result, the water complex becomes less stable in the relaxed S1 state despite decreased Pauli repulsion. Stronger binding of the anisole–ammonia complex following electronic excitation is more nuanced and results from counteracting shifts in the repulsive (exchange) and attractive (electrostatic, induction and dispersion) forces. In particular, we show that the formation of additional binding N–H···π contacts in the relaxed S1 geometry is possible due to reduced Pauli repulsion in the excited state. The SAPT(CAS) interaction energies have been validated against the coupled cluster (CC) results and experimentally determined shifts of the S1 ← S0 anisole band. While for the hydrogen-bonded anisole–water dimer SAPT(CAS) and CC shifts are in excellent agreement, for ammonia SAPT(CAS) is only qualitatively correct.

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

Abstract: In contrast to standard DFT predictions, 2-naphthol is shown to dock on the oxygen of anisole, with excitation-dependent angular geometry.

Cited by 3 publications

References 85 publications

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

Regularities and Anomalies in Neon Matrix Shifts of Hydrogen-Bonded O–H Stretching Fundamentals

Anisole–Water and Anisole–Ammonia Complexes in Ground and Excited (S₁) States: A Multiconfigurational Symmetry-Adapted Perturbation Theory (SAPT) Study

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

Abstract: In contrast to standard DFT predictions, 2-naphthol is shown to dock on the oxygen of anisole, with excitation-dependent angular geometry.

Cited by 3 publications

References 85 publications

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

Regularities and Anomalies in Neon Matrix Shifts of Hydrogen-Bonded O–H Stretching Fundamentals

Anisole–Water and Anisole–Ammonia Complexes in Ground and Excited (S1) States: A Multiconfigurational Symmetry-Adapted Perturbation Theory (SAPT) Study

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Product

Resources

About

Anisole–Water and Anisole–Ammonia Complexes in Ground and Excited (S₁) States: A Multiconfigurational Symmetry-Adapted Perturbation Theory (SAPT) Study