Double Proton Transfer Across a Table: The Formic Acid Dimer–Fluorobenzene Complex

Li, Weixing; Tikhonov, Denis S.; Schnell, Melanie

doi:10.1002/anie.202108242

Cited by 10 publications

(8 citation statements)

References 33 publications

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“…At first slight, the E HB , and E HB Eff and the resulting Δ E 01 values obtained depend strongly on the functionals used, and the precision of the theoretical results appear to be too low to reproduce the experimental data. Similar variations in the theoretical results of proton transfer were reported for the dimers of formic acid and maloic acid, formic acid dimer with fluorobenzene, and also in the large amplitude motion of thiophenol dimers [14,43,45] . Generally, while some usual trend could be predicted, the extremely accurate results provided by rotational spectroscopy are very difficult to reproduce computationally.…”

Section: Resultssupporting

confidence: 65%

“…The proton transfer dynamics was then calculated using the publicly available Python code [27] . This procedure was used recently for a complex consists of a formic acid dimer and a fluorobenzene molecule [43] . For the reaction coordinate, the following expression was used:

true ξ = (() r (O - H) + r (O - H) - r (O \cdot \cdot \cdot H O) - r (O \cdot \cdot \cdot H O)) / 2 \sqrt{2}

…”

Section: Resultsmentioning

confidence: 99%

“…Similar variations in the theoretical results of proton transfer were reported for the dimers of formic acid and maloic acid, formic acid dimer with fluorobenzene, and also in the large amplitude motion of thiophenol dimers. [14,43,45] Generally, while some usual trend could be predicted, the extremely accurate results provided by rotational spectroscopy are very difficult to reproduce computationally.…”

Section: Chemphyschemmentioning

confidence: 99%

“…[27] This procedure was used recently for a complex consists of a formic acid dimer and a fluorobenzene molecule. [43] For the reaction coordinate, the following expression was used:…”

Section: Chemphyschemmentioning

confidence: 99%

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Rotational Spectroscopy of 2‐Furoic Acid and Its Dimer: Conformational Distribution and Double Proton Tunneling

Insausti

Qinye

et al. 2022

ChemPhysChem

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Structural and tunneling properties of the 2-furoic acid (FA) monomer and dimer were investigated using rotational spectroscopy and DFT calculations. CREST, a conformational ensemble space exploration tool, was used to identify all possible lowenergy conformations of the FA monomer and dimer, followed by the DFT geometry optimization and harmonic frequency calculations. Broadband rotational spectra in the 2-6 and 8-12 GHz regions were recorded in a supersonic jet expansion. The monomeric FA was found to exist dominantly as three different conformers: I, II, and III in a jet, with I and II taking on the cis-COOH configuration while III having the trans-COOH configuration. For the FA dimer, only the I-II conformer was observed experimentally, whereas the symmetric I-I and II-II conformers were not observed because of their zero dipole moments. The analysis of the splittings in the rotational transitions of I-II allowed one to extract the tunneling splitting to be 1056.0(12) MHz. The barrier height was determined to be ~442 cm À 1 using the scaled potential energy scans at several different levels of theory.

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Section: Resultssupporting

confidence: 65%

true ξ = (() r (O - H) + r (O - H) - r (O \cdot \cdot \cdot H O) - r (O \cdot \cdot \cdot H O)) / 2 \sqrt{2}

…”

Section: Resultsmentioning

confidence: 99%

Section: Chemphyschemmentioning

confidence: 99%

“…[27] This procedure was used recently for a complex consists of a formic acid dimer and a fluorobenzene molecule. [43] For the reaction coordinate, the following expression was used:…”

Section: Chemphyschemmentioning

confidence: 99%

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Rotational Spectroscopy of 2‐Furoic Acid and Its Dimer: Conformational Distribution and Double Proton Tunneling

Insausti

Qinye

et al. 2022

ChemPhysChem

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“…[16] The double proton transfer dynamics in carboxylic acid hetero and homo dimers was extensively characterized by the combination of rotational spectroscopy and the flexible model. [17] Recently, microwave spectroscopy has revealed the influence of neighboring molecules on the proton transfer dynamics of the formic acid dimer, [18] which has been rationalized through solving the one-dimensional Schrödinger equation obtained from a simplistic ab initio computational procedure. [19] In this study, we report the role-exchanging tunneling dynamics observed for a homochiral CD dimer using broad-band chirped-pulse Fourier transform microwave (CP-FTMW) spectroscopy, [20] also known as Molecular Rotational Resonance (MRR) spectroscopy.…”

mentioning

confidence: 99%

Hydrogen‐Atom Tunneling in a Homochiral Environment

et al. 2023

Self Cite

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The role‐exchanging concerted torsional motion of two hydrogen atoms in the homochiral dimer of trans‐1,2‐cyclohexanediol was characterized through a combination of broadband rotational spectroscopy and theoretical modeling. The results reveal that the concerted tunneling motion of the hydrogen atoms leads to the inversion of the sign of the dipole moment components along the a and b principal axes, due to the interchange motion that cooperatively breaks and reforms one intermolecular hydrogen bond. This motion is also coupled with two acceptor switching motions. The energy difference between the two ground vibrational states arising from this tunneling motion was determined to be 29.003(2) MHz. The corresponding wavefunctions suggest that the two hydrogen atoms are evenly delocalized on two equivalent potential wells, which differs from the heterochiral case where the hydrogen atoms are confined in separate wells, as the permutation‐inversion symmetry breaks down. This intriguing contrast in hydrogen‐atom behavior between homochiral and heterochiral environments could further illuminate our understanding of the role of chirality in intermolecular interactions and dynamics.

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Gestapelt, nicht geklebt: Enthüllung der π→π*‐Wechselwirkung mithilfe des Benzofuran‐Formaldehyd‐Komplexes

Spada

Alessandrini

et al. 2021

Angewandte Chemie

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Der 1:1-Benzofuran-Formaldehyd-Komplex wurde als Modellsystem für p!p*-Wechselwirkungen in supramolekularen Umgebungen mit heteroaromatischen Ringen und Carbonylgruppen gewählt. Die Strategie einer gemeinsamen "Rotationsspektroskopie-Quantenchemie"-Analyse enthüllt die Rolle dominanter intermolekularer p!p*-Wechselwirkungen in solchen Addukten. Die Untersuchung der intermolekularen Potentialfläche identifiziert 14 tiefliegende Minima, wobei 4 gestapelte Isomere stabiler sind als die durch Wasserstoffbrücken oder "freies Elektronenpaar"!p-Wechselwirkungen verbundene. Alle lokalen Minima sind nur lose durch Übergangszustände getrennt, was unter den experimentellen Bedingungen eine effektive Relaxation zum globalen Minimum erwarten lässt. Der Nachweis nur einer Spezies, die dank Berechnung genauer spektroskopischer Parameter und Charakterisierung von 11 Isotopologen eindeutig zugeordnet werden konnte, bestätigt dies. Die große Isotopologenanzahl ermçglichte die Bestimmung der ersten semi-experimentellen Gleichgewichtsstruktur für einen Molekülkomplex dieser Grçßenordnung.Aromatische Verbindungen spielen eine Schlüsselrolle bei der Strukturausbildung von Biomolekülen und beeinflussen Prozesse, die mit Ursprung und Entwicklung des Lebens (Photosynthese, [1] Informationsspeicherung, [2] DNA-Replikation [3] etc.) diskutiert werden. Dabei sind durch nicht-kovalente Wechselwirkungen (NCI) vermittelte und von aromatischen Einheiten beherrschte Prozesse von grçßter Bedeutung, [4] die so verschiedene Bereiche wie molekulare Erkennung, [5] Katalyse, [5c, 6] Crystal Engineering [7] und Arzneimittelverabreichung abdecken. [8] Die Vielseitigkeit der aromatischen Gruppen spiegelt sich in Anzahl, Arten und Spezifität der NCI wider. [9] Darunter sind Heteroaromaten besonders wichtig, da sie als Teil der Nukleobasen Bausteine des Lebens sind und eine zentrale Rolle in der medizinischen Chemie spielen. [10] In diesem Bereich ist das Benzofuran (BZF), welches das Heteroaromaten-Grundgerüst für eine große Reihe von Verbindungen mit pharmakologischen Aktivitäten bildet, [11] interessant. In BZF-Derivaten konkurrieren das p-System und das freie s-Elektronenpaar des Sauerstoffs bei der Bildung von NCIs. [12] Ein Beispiel ist die Komplexbildung des aktivierten menschlichen Blutgerinnungsfaktors X (FXa) mit (S)-2-Cyano-1-(2-methylbenzofuran-5-yl)-3-(2-oxo-1-(2-oxo-2-(pyrrolidin-1-yl) ethyl)azepan-3-yl)guanidin (PDB:3HPT [13] YET 2.D-Ligand). Die in der Proteindatenbank (PDB) verçffentlichte Struktur [14] zeigt enge intermolekulare Kontakte (drei davon mit Abständen von weniger als 3.6 ) zwischen dem BZF und den Carbonylanteilen (siehe Abbildung 1). Während intra-und intermolekulare Wechselwirkungen in Biomolekülen von großem Abbildung 1. Bereich der PDB:3HPT [13,14] -Struktur (Einzelheiten im Text) mit engen intermolekularen Kontakten zwischen einem (2-Methyl)-BZF-Teil des YET 2.D-Liganden und einer Carbonylgruppe. Die Struktur wurde mit der Software Chimera 1.14 visualisiert.

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Double Proton Transfer Across a Table: The Formic Acid Dimer–Fluorobenzene Complex

Cited by 10 publications

References 33 publications

Rotational Spectroscopy of 2‐Furoic Acid and Its Dimer: Conformational Distribution and Double Proton Tunneling

Rotational Spectroscopy of 2‐Furoic Acid and Its Dimer: Conformational Distribution and Double Proton Tunneling

Hydrogen‐Atom Tunneling in a Homochiral Environment

Gestapelt, nicht geklebt: Enthüllung der π→π*‐Wechselwirkung mithilfe des Benzofuran‐Formaldehyd‐Komplexes

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