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Tautomerism and Proton Transfer Related Phenomena
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Tautomerism and Proton Transfer Related Phenomena

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Physical Chemistry".

Deadline for manuscript submissions: closed (31 December 2021) | Viewed by 27572

Special Issue Editor

Prof. Dr. Liudmil Antonov

E-Mail Website
Guest Editor
Institute of Electronics Bulgarian Academy of Sciences, 72 Tzarigradsko chaussee blvd., 1784 Sofia, Bulgaria
Interests: tautomerism; proton transfer; hydrogen bonding; molecular switches; molecular sensors; dye chemistry; solvent effect; photo-, halo- and thermochromism; optical spectroscopy; computational chemistry; photochemistry

Special Issue Information

Dear Colleagues,

The aim of this Special Issue is to collect together scientific works related to the prototropic tautomerism and proton transfer in ground and excited state in the gas phase, solution and solid state. Experimental and theoretical studies describing the structural and environmental (solvent, temperature, acidity, irradiation) effects on the tautomeric equilibrium and the dynamics of proton transfer are welcome. Special emphasis will be given to conventional and high-tech dyes, molecular sensors, switches and machines, biologically active compounds, natural products, reaction intermediates and all other cases in organic chemistry, where prototropic tautomerism and proton transfer are involved.

Prof. Dr. Liudmil Antonov
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Molecules is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • tautomerism
  • proton transfer
  • solvent and temperature effects
  • structure and spectra
  • steady-state and time-dependent methods
  • molecular spectroscopy (UV-Vis, IR/Raman, NMR)
  • theoretical description
  • physical chemistry
  • quantum chemistry

Published Papers (7 papers)

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Research

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23 pages, 7476 KiB  
Article
Double Proton Tautomerism via Intra- or Intermolecular Pathways? The Case of Tetramethyl Reductic Acid Studied by Dynamic NMR: Hydrogen Bond Association, Solvent and Kinetic H/D Isotope Effects
by Hans-Heinrich Limbach, Simone Baumgärtner, Roland Franke, Ferdinand Männle, Gerd Scherer and Gleb S. Denisov
Molecules 2021, 26(14), 4373; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26144373 - 20 Jul 2021
Cited by 6 | Viewed by 2054
Abstract
Using dynamic liquid-state NMR spectroscopy a degenerate double proton tautomerism was detected in tetramethyl reductic acid (TMRA) dissolved in toluene-d8 and in CD2Cl2. Similar to vitamin C, TMRA belongs to the class of reductones of biologically important [...] Read more.
Using dynamic liquid-state NMR spectroscopy a degenerate double proton tautomerism was detected in tetramethyl reductic acid (TMRA) dissolved in toluene-d8 and in CD2Cl2. Similar to vitamin C, TMRA belongs to the class of reductones of biologically important compounds. The tautomerism involves an intramolecular HH transfer that interconverts the peripheric and the central positions of the two OH groups. It is slow in the NMR time scale around 200 K and fast at room temperature. Pseudo-first-order rate constants of the HH transfer and of the HD transfer after suitable deuteration were obtained by line shape analyses. Interestingly, the chemical shifts were found to be temperature dependent carrying information about an equilibrium between a hydrogen bonded dimer and a monomer forming two weak intramolecular hydrogen bonds. The structures of the monomer and the dimer are discussed. The latter may consist of several rapidly interconverting hydrogen-bonded associates. A way was found to obtain the enthalpies and entropies of dissociation, which allowed us to convert the pseudo-first-order rate constants of the reaction mixture into first-order rate constants of the tautomerization of the monomer. Surprisingly, these intrinsic rate constants were the same for toluene-d8 and CD2Cl2, but in the latter solvent more monomer is formed. This finding is attributed to the dipole moment of the TMRA monomer, compensated in the dimer, and to the larger dielectric constant of CD2Cl2. Within the margin of error, the kinetic HH/HD isotope effects were found to be of the order of 3 but independent of temperature. That finding indicates a stepwise HH transfer involving a tunnel mechanism along a double barrier pathway. The Arrhenius curves were described in terms of the Bell–Limbach tunneling model. Full article
(This article belongs to the Special Issue Tautomerism and Proton Transfer Related Phenomena)
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15 pages, 5539 KiB  
Article
Hydrogen-Bonded Cyclic Dimers at Large Compression: The Case of 1H-pyrrolo[3,2-h]quinoline and 2-(2′-pyridyl)pyrrole
by Dominik Kurzydłowski, Taisiia Chumak, Jakub Rogoża and Arkadiusz Listkowski
Molecules 2021, 26(13), 3802; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26133802 - 22 Jun 2021
Cited by 1 | Viewed by 1999
Abstract
1H-pyrrolo[3,2-h]qinoline (PQ) and 2-(2′-pyridyl)pyrrole (PP) are important systems in the study of proton-transfer reactions. These molecules possess hydrogen bond donor (pyrrole) and acceptor (pyridine) groups, which leads to the formation of cyclic dimers in their crystals. Herein, we present [...] Read more.
1H-pyrrolo[3,2-h]qinoline (PQ) and 2-(2′-pyridyl)pyrrole (PP) are important systems in the study of proton-transfer reactions. These molecules possess hydrogen bond donor (pyrrole) and acceptor (pyridine) groups, which leads to the formation of cyclic dimers in their crystals. Herein, we present a joint experimental (Raman scattering) and computational (DFT modelling) study on the high-pressure behaviour of PQ and PP molecular crystals. Our results indicate that compression up to 10 GPa (100 kbar) leads to considerable strengthening of the intermolecular hydrogen bond within the cyclic dimers. However, the intramolecular N–H∙∙∙N interaction is either weakly affected by pressure, as witnessed in PQ, or weakened due to compression-induced distortions of the molecule, as was found for PP. Therefore, we propose that the compression of these systems should facilitate double proton transfer within the cyclic dimers of PQ and PP, while intramolecular transfer should either remain unaffected (for PQ) or weakened (for PP). Full article
(This article belongs to the Special Issue Tautomerism and Proton Transfer Related Phenomena)
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34 pages, 27953 KiB  
Article
Unraveling the Effects of Co-Crystallization on the UV/Vis Absorption Spectra of an N-Salicylideneaniline Derivative. A Computational RI-CC2 Investigation
by Jean Quertinmont, Tom Leyssens, Johan Wouters and Benoît Champagne
Molecules 2020, 25(19), 4512; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules25194512 - 01 Oct 2020
Cited by 1 | Viewed by 2040
Abstract
This work aims at unraveling the effects of co-crystallization on the optical properties of an N-salicylideneaniline-derived molecular switch transforming between an enol and a keto form. This is achieved by way of a two-step multi-scale method where (i) the molecular geometry and [...] Read more.
This work aims at unraveling the effects of co-crystallization on the optical properties of an N-salicylideneaniline-derived molecular switch transforming between an enol and a keto form. This is achieved by way of a two-step multi-scale method where (i) the molecular geometry and unit cell parameters are optimized using a periodic boundary conditions density functional theory method and (ii) the optical properties are computed for a selection of clusters embedded in an array of point-charges that reproduce the crystal field electronic potential. The optical properties (vertical excitation energies and oscillator strengths) are obtained at the RI-CC2/def2-TZVPD level of approximation. This method allows us to decompose the effects of co-crystallization into (i) indirect effects, the geometry changes of the chromophore due to crystal packing with the coformer, and (ii) direct ones, the polarization due to the interacting coformer and to the crystal field. For the former effects, variations of a crucial torsion angle lead to modification of the π-conjugation and therefore to the decrease or increase of the excitation energies. About the latter, they are antagonistic: (i) the coformer is not directly involved in the excitations but its polarization decreases the excitation energies while (ii) the crystal field has the opposite effect. For the co-crystals with succinic and fumaric acids, combining these direct and indirect effects leads to a hypsochromic shift of the first absorption band with respect to the reference crystal, in agreement with experimental data. Full article
(This article belongs to the Special Issue Tautomerism and Proton Transfer Related Phenomena)
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20 pages, 2314 KiB  
Article
13C CPMAS NMR as a Tool for Full Structural Description of 2-Phenyl Substituted Imidazoles That Overcomes the Effects of Fast Tautomerization
by Nikola Burdzhiev, Anife Ahmedova, Boris Borrisov and Robert Graf
Molecules 2020, 25(17), 3770; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules25173770 - 19 Aug 2020
Cited by 4 | Viewed by 2600
Abstract
Tautomerization of 2-phenylimidazolecarbaldehydes has not been studied in detail so far, although this process is a well-known phenomenon for imidazole derivatives. That is why we focus our study on a series of 2-phenylimidazolecarbaldehydes and their parent alcohols that were synthesized and studied by [...] Read more.
Tautomerization of 2-phenylimidazolecarbaldehydes has not been studied in detail so far, although this process is a well-known phenomenon for imidazole derivatives. That is why we focus our study on a series of 2-phenylimidazolecarbaldehydes and their parent alcohols that were synthesized and studied by detailed 1H and 13C NMR in solution and in the solid state. The apparent problem is that the fast tautomerization impedes the full structural description of the compounds by conventional 13C NMR measurements. Indeed, the 13C NMR spectra in solution exhibit poor resolution, and in most cases, signals from the imidazole ring are not detectable. To avoid this problem, we used 13C CP-MAS NMR as an alternative spectroscopic method for unambiguous spectroscopic characterization of the studied series of 2-phenylimidazoles. The data were analyzed in combination with quantum chemical DFT-GIAO methods by considering the tautomerization process and the intermolecular interactions. The DFT (B3LYP/6-31G(d,p)) calculations allowed to identify and suggest the preferred tautomer in the gas phase and in DMSO solvent, which for alcohols are (2-phenyl-1H-imidazol-4-yl)methanol and its analogs, and for the aldehydes are the 2-phenyl-1H-imidazole-5-carbaldehydes. The gas-phase calculated energy differences between the two possible tautomeric forms are in the range 0.645–1.415 kcal/mol for the alcohols and 2.510–3.059 kcal/mol for the aldehydes. In the DMSO solvent, however, for all compounds, the calculated energy differences go below 1.20 kcal/mol. These data suggest that both tautomeric forms of the studied 2-phenylimidazoles can be present in solution at room temperature. Our data from detailed 2D NMR measurements in the solid state (1H-13C HETCOR and 1H-1H double-quantum coherence MAS NMR) suggested that also in the solid state both tautomers coexist in different crystalline domains. This fact does not obscure the 13C CP-MAS NMR spectra of the studied 2-phenyl substituted imidazoles and suggests this spectroscopic method as a powerful tool for a complete structural description of tautomeric systems with aromatic conjugation. Full article
(This article belongs to the Special Issue Tautomerism and Proton Transfer Related Phenomena)
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13 pages, 2227 KiB  
Article
Tautomerism and Self-Association in the Solution of New Pinene-Bipyridine and Pinene-Phenanthroline Derivatives
by Atena B. Solea, Ivan Cornu, Vera Deneva, Aurelien Crochet, Katharina M. Fromm, Liudmil Antonov, Christophe Allemann and Olimpia Mamula
Molecules 2020, 25(2), 298; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules25020298 - 11 Jan 2020
Viewed by 3712
Abstract
Two novel pinene-type ligands have been synthesized and their tautomeric and self-associating behavior studied in solution and in the solid state. The first ligand, an acetylated derivative of 5,6-pinene-bipyridine, displays keto-enol tautomerism in solution. This tautomeric equilibrium was studied by NMR and UV-Vis [...] Read more.
Two novel pinene-type ligands have been synthesized and their tautomeric and self-associating behavior studied in solution and in the solid state. The first ligand, an acetylated derivative of 5,6-pinene-bipyridine, displays keto-enol tautomerism in solution. This tautomeric equilibrium was studied by NMR and UV-Vis spectroscopy in various solvents, and the results were compared with the ones obtained through DFT calculations. The second ligand was obtained by an unusual oxidation of the phenanthroline unit of a pinene-phenanthroline derivative. This compound exists as a single tautomer in solution and aggregates both in solution (as observed by NMR) and in the solid state through H-bonding as observed by X-ray structure determination and confirmed by DFT studies. Full article
(This article belongs to the Special Issue Tautomerism and Proton Transfer Related Phenomena)
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14 pages, 798 KiB  
Article
Tautomerism in Azo and Azomethyne Dyes: When and If Theory Meets Experiment
by Liudmil Antonov
Molecules 2019, 24(12), 2252; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules24122252 - 17 Jun 2019
Cited by 32 | Viewed by 3676
Abstract
The performance of 26 hybrid density functionals was tested against a tautomeric dataset (TautData), containing experimental information for the keto-enol tautomeric equilibrium in 16 tautomeric azodyes and Schiff bases in cyclohexane, carbon tetrachloride and acetonitrile. The results have shown that MN12-SX, BHandH and [...] Read more.
The performance of 26 hybrid density functionals was tested against a tautomeric dataset (TautData), containing experimental information for the keto-enol tautomeric equilibrium in 16 tautomeric azodyes and Schiff bases in cyclohexane, carbon tetrachloride and acetonitrile. The results have shown that MN12-SX, BHandH and M06-2X can be used to describe the tautomeric state of the core structures in the frame of ~0.5 kcal/mol error and correctly predict the tautomeric state in respect of dominating tautomeric form. Among them MN12-SX is the best performer, although it fails to describe the nonplanarity of some of the enol tautomers. The same experimental dataset was used to develop and test a special DFT functional (TautLYP) aimed at describing the tautomeric state in azo- and azomethyne compounds in solution when nonspecific solvents are used. Full article
(This article belongs to the Special Issue Tautomerism and Proton Transfer Related Phenomena)
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Review

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18 pages, 4524 KiB  
Review
Excited-State Intramolecular Proton Transfer: A Short Introductory Review
by Hem C. Joshi and Liudmil Antonov
Molecules 2021, 26(5), 1475; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26051475 - 09 Mar 2021
Cited by 102 | Viewed by 10251
Abstract
In this short review, we attempt to unfold various aspects of excited-state intramolecular proton transfer (ESIPT) from the studies that are available up to date. Since Weller’s discovery of ESIPT in salicylic acid (SA) and its derivative methyl salicylate (MS), numerous studies have [...] Read more.
In this short review, we attempt to unfold various aspects of excited-state intramolecular proton transfer (ESIPT) from the studies that are available up to date. Since Weller’s discovery of ESIPT in salicylic acid (SA) and its derivative methyl salicylate (MS), numerous studies have emerged on the topic and it has become an attractive field of research because of its manifold applications. Here, we discuss some critical aspects of ESIPT and tautomerization from the mechanistic viewpoint. We address excitation wavelength dependence, anti-Kasha ESIPT, fast and slow ESIPT, reversibility and irreversibility of ESIPT, hydrogen bonding and geometrical factors, excited-state double proton transfer (ESDPT), concerted and stepwise ESDPT. Full article
(This article belongs to the Special Issue Tautomerism and Proton Transfer Related Phenomena)
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