Solvent‐Assisted Prototopic Switching of Norharmane Along Hydrogen‐Bonded Network: Assessing the Precise Length of Network.
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| Title: | Solvent‐Assisted Prototopic Switching of Norharmane Along Hydrogen‐Bonded Network: Assessing the Precise Length of Network. |
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| Authors: | Paul, Suvendu1 (AUTHOR) paul.suvendu2016@gmail.com, Dey, Nilanjan1 (AUTHOR) nilanjandey.iisc@gmail.com |
| Source: | Journal of Physical Organic Chemistry. Feb2025, Vol. 38 Issue 2, p1-9. 9p. |
| Subjects: | Density functional theory, Water clusters, Tautomerism, Hydrogen bonding, Excited states |
| Abstract: | In this article, the proton transfer dynamics along a stable norharmane•(H2O)n (n = 2–4) hydrogen‐bonded cluster on conversion from the neutral to cationic form of norharmane (NHM) in water medium was demonstrated experimentally and theoretically. The distinct absorption and emission bands of different prototropic forms of NHM are well‐known in the literature. Initially, the conversion from neutral to cationic form of NHM on moving from a polar aprotic (acetonitrile) to a polar protic (water) solvent was ensured by steady‐state absorption and fluorescence studies. The analysis of IR spectra and steady‐state anisotropy data of NHM confirmed the possibility of the formation of a hydrogen‐bonded network in the presence of water. The length of the network was explored and assumed by extensive Density Functional Theory (DFT) calculations. Then, by time‐dependent density functional theory (TD‐DFT), the excited state proton transfer (ESPT) pathway was established interrogating the NHM‐water cluster with different numbers of water molecules. The theoretical analysis assured that the NHM•(H2O)2 cluster was incapable of maintaining the stable hydrogen bonding wire in the course of the ESPT mechanism. Rather, NHM•(H2O)3 and NHM•(H2O)4 clusters were simultaneously involved in operating the ESPT mechanism. The NHM•(H2O)4 cluster was more feasible to carry out the proton transfer than the NHM•(H2O)3 cluster. To the best of our knowledge, this was possibly the first theoretical evidence behind the conversion from neutral to cationic form of NHM via the formation of a hydrogen‐bonded network. [ABSTRACT FROM AUTHOR] |
| Copyright of Journal of Physical Organic Chemistry is the property of Wiley-Blackwell and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.) | |
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| Header | DbId: egs DbLabel: Engineering Source An: 183920635 AccessLevel: 6 PubType: Academic Journal PubTypeId: academicJournal PreciseRelevancyScore: 0 |
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| Items | – Name: Title Label: Title Group: Ti Data: Solvent‐Assisted Prototopic Switching of Norharmane Along Hydrogen‐Bonded Network: Assessing the Precise Length of Network. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Paul%2C+Suvendu%22">Paul, Suvendu</searchLink><relatesTo>1</relatesTo> (AUTHOR)<i> paul.suvendu2016@gmail.com</i><br /><searchLink fieldCode="AR" term="%22Dey%2C+Nilanjan%22">Dey, Nilanjan</searchLink><relatesTo>1</relatesTo> (AUTHOR)<i> nilanjandey.iisc@gmail.com</i> – Name: TitleSource Label: Source Group: Src Data: <searchLink fieldCode="JN" term="%22Journal+of+Physical+Organic+Chemistry%22">Journal of Physical Organic Chemistry</searchLink>. Feb2025, Vol. 38 Issue 2, p1-9. 9p. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Density+functional+theory%22">Density functional theory</searchLink><br /><searchLink fieldCode="DE" term="%22Water+clusters%22">Water clusters</searchLink><br /><searchLink fieldCode="DE" term="%22Tautomerism%22">Tautomerism</searchLink><br /><searchLink fieldCode="DE" term="%22Hydrogen+bonding%22">Hydrogen bonding</searchLink><br /><searchLink fieldCode="DE" term="%22Excited+states%22">Excited states</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: In this article, the proton transfer dynamics along a stable norharmane•(H2O)n (n = 2–4) hydrogen‐bonded cluster on conversion from the neutral to cationic form of norharmane (NHM) in water medium was demonstrated experimentally and theoretically. The distinct absorption and emission bands of different prototropic forms of NHM are well‐known in the literature. Initially, the conversion from neutral to cationic form of NHM on moving from a polar aprotic (acetonitrile) to a polar protic (water) solvent was ensured by steady‐state absorption and fluorescence studies. The analysis of IR spectra and steady‐state anisotropy data of NHM confirmed the possibility of the formation of a hydrogen‐bonded network in the presence of water. The length of the network was explored and assumed by extensive Density Functional Theory (DFT) calculations. Then, by time‐dependent density functional theory (TD‐DFT), the excited state proton transfer (ESPT) pathway was established interrogating the NHM‐water cluster with different numbers of water molecules. The theoretical analysis assured that the NHM•(H2O)2 cluster was incapable of maintaining the stable hydrogen bonding wire in the course of the ESPT mechanism. Rather, NHM•(H2O)3 and NHM•(H2O)4 clusters were simultaneously involved in operating the ESPT mechanism. The NHM•(H2O)4 cluster was more feasible to carry out the proton transfer than the NHM•(H2O)3 cluster. To the best of our knowledge, this was possibly the first theoretical evidence behind the conversion from neutral to cationic form of NHM via the formation of a hydrogen‐bonded network. [ABSTRACT FROM AUTHOR] – Name: AbstractSuppliedCopyright Label: Group: Ab Data: <i>Copyright of Journal of Physical Organic Chemistry is the property of Wiley-Blackwell and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.) |
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| RecordInfo | BibRecord: BibEntity: Identifiers: – Type: doi Value: 10.1002/poc.4678 Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 9 StartPage: 1 Subjects: – SubjectFull: Density functional theory Type: general – SubjectFull: Water clusters Type: general – SubjectFull: Tautomerism Type: general – SubjectFull: Hydrogen bonding Type: general – SubjectFull: Excited states Type: general Titles: – TitleFull: Solvent‐Assisted Prototopic Switching of Norharmane Along Hydrogen‐Bonded Network: Assessing the Precise Length of Network. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Paul, Suvendu – PersonEntity: Name: NameFull: Dey, Nilanjan IsPartOfRelationships: – BibEntity: Dates: – D: 01 M: 02 Text: Feb2025 Type: published Y: 2025 Identifiers: – Type: issn-print Value: 08943230 Numbering: – Type: volume Value: 38 – Type: issue Value: 2 Titles: – TitleFull: Journal of Physical Organic Chemistry Type: main |
| ResultId | 1 |
