کد مقاله کد نشریه سال انتشار مقاله انگلیسی نسخه تمام متن
1230037 1495198 2017 8 صفحه PDF دانلود رایگان
عنوان انگلیسی مقاله ISI
Solvent-dependent dynamics of hydrogen bonding structure 5-(methylthio)-1, 3, 4-thiadiazole-2(3H)-thione as determined by Raman spectroscopy and theoretical calculation
ترجمه فارسی عنوان
پویایی حلال وابسته به ساختار پیوند هیدروژنی 5- (متیل) -1، 3، 4، thiadiazole-2 (3H) -thione توسط طیف سنجی رامان و محاسبات نظری تعیین
کلمات کلیدی
5- (Methylthio) -1،3،4-Thiadiazole-2 (3H) -thione؛ پیوند هیدروژنی بین مولکولی؛ طیف سنجی رامان؛ محاسبه نظری؛ دینامیک ساختاری
موضوعات مرتبط
مهندسی و علوم پایه شیمی شیمی آنالیزی یا شیمی تجزیه
چکیده انگلیسی


• The ground state structures of MTTN in solvents have been determined via Raman spectroscopic experiments and DFT calculation.
• The MTTN in different solvents can be characterized as MTTN(solvent)n (solvent=CH3CN, CH3OH and H2O; n=1, 2, 3) clusters.
• Hydrogen bond (H-bond) interactions between MTTN and solvents significantly contribute to different Raman intensity patterns.
• The intermolecular >NH ⋯ O and >NH ⋯ N H-bond underlines an significant spectra differences of MTTN in CH3CN, CH3OH and H2O.

The vibration spectra of 5-(methylthio)-1,3,4-thiadiazole-2(3H)-thione (MTTN) in acetonitrile (CH3CN), methanol (CH3OH) and water (H2O) solvents were collected and evaluated via deuterium isotopic substitution Raman spectroscopic experiments. These experiments were combined with the quantum chemical theoretical calculations using the PCM solvent model and normal mode analysis. The results confirmed that the MTTN in CH3CN, CH3OH and H2O have hydrogen bonding (H-bonding) MTTN(solvent)n clusters that produce significantly different Raman intensity patterns in different solvents. Combined with the normal Raman assignment, most resonance Raman spectra were assigned to the vibration modes of the H-bonding MTTN(CH3CN), MTTN(CH3OH)3 and MTTN(H2O)3 clusters in CH3CN, CH3OH and H2O. The theoretically-predicted frequencies and intensities in different surrounding environments enabled reliable assignments of Raman bands. The intermolecular > NH ⋯ O and > NH ⋯ N H-bonding interactions are key constituents of stable thione structures in MTTN. This underlines the significant structural differences of MTTN in CH3CN, CH3OH and H2O. H-bonding perturbation of MTTN reveal important insights about the intermolecular excited state proton transfer (ESPT) reaction mechanisms in the Franck-Condon region structural dynamics of the thione → thiol tautomer in CH3OH and H2O.

MTTN(solvent)n clusters. Hydrogen bonds are key constituents of stable thione structure of MTTN, and external perturbations of hydrogen bond may reveal important insights about the intermolecular excited state proton transfer (ESPT) reaction mechanisms in the Franck-Condon region structural dynamics of thione → thiol tautomer in CH3OH and H2O.Figure optionsDownload as PowerPoint slide

ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy - Volume 171, 15 January 2017, Pages 470–477
نویسندگان
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