Julian Radicke, Vanessa Jerschabek, Haleh Hashemi Haeri, Muhammad Abu Bakar, Dariush Hinderberger, Jörg Kressler, Karsten Busse
{"title":"[EMIm][OAc]中溶解的S4N4和(SN)x的核磁共振和电子顺磁共振光谱表征","authors":"Julian Radicke, Vanessa Jerschabek, Haleh Hashemi Haeri, Muhammad Abu Bakar, Dariush Hinderberger, Jörg Kressler, Karsten Busse","doi":"10.1021/acs.jpcb.5c00294","DOIUrl":null,"url":null,"abstract":"<p><p>This work focuses on the reaction mechanism of poly(sulfur nitride) ((SN)<sub><i>x</i></sub>, (S<sup>15</sup>N)<sub><i>x</i></sub>), with the ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate [EMIm][OAc]. We compare this with the reaction of the IL with S<sub>4</sub>N<sub>4</sub> or its <sup>15</sup>N-labeled form S<sub>4</sub><sup>15</sup>N<sub>4</sub>, a precursor for the synthesis of (SN)<sub><i>x</i></sub> and (S<sup>15</sup>N)<sub><i>x</i></sub>. After purification of the S<sub>4</sub>N<sub>4</sub>-IL- and S<sub>4</sub><sup>15</sup>N<sub>4</sub>-IL systems via column chromatography, we characterized the reaction products with <sup>1</sup>H, <sup>13</sup>C, and <sup>15</sup>N nuclear magnetic resonance spectroscopy and with electron spray ionization time-of-flight mass spectrometry. Furthermore, time-resolved electron paramagnetic resonance spectroscopy and time-resolved ultraviolet-visible spectroscopy were carried out. Thus, radical intermediates were detected, which were consumed with reaction time. Finally, we postulate a reaction mechanism for the S<sub>4</sub>N<sub>4</sub>-IL- and S<sub>4</sub><sup>15</sup>N<sub>4</sub>-IL systems and compare this with the respective data for the (SN)<sub><i>x</i></sub> -IL- and (S<sup>15</sup>N)<sub><i>x</i></sub>-IL-systems.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":"129 16","pages":"4063-4077"},"PeriodicalIF":2.9000,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12035862/pdf/","citationCount":"0","resultStr":"{\"title\":\"Nuclear Magnetic Resonance- and Electron Paramagnetic Resonance Spectroscopic Characterization of S<sub>4</sub>N<sub>4</sub> and (SN)<sub><i>x</i></sub> Dissolved in [EMIm][OAc].\",\"authors\":\"Julian Radicke, Vanessa Jerschabek, Haleh Hashemi Haeri, Muhammad Abu Bakar, Dariush Hinderberger, Jörg Kressler, Karsten Busse\",\"doi\":\"10.1021/acs.jpcb.5c00294\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>This work focuses on the reaction mechanism of poly(sulfur nitride) ((SN)<sub><i>x</i></sub>, (S<sup>15</sup>N)<sub><i>x</i></sub>), with the ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate [EMIm][OAc]. We compare this with the reaction of the IL with S<sub>4</sub>N<sub>4</sub> or its <sup>15</sup>N-labeled form S<sub>4</sub><sup>15</sup>N<sub>4</sub>, a precursor for the synthesis of (SN)<sub><i>x</i></sub> and (S<sup>15</sup>N)<sub><i>x</i></sub>. After purification of the S<sub>4</sub>N<sub>4</sub>-IL- and S<sub>4</sub><sup>15</sup>N<sub>4</sub>-IL systems via column chromatography, we characterized the reaction products with <sup>1</sup>H, <sup>13</sup>C, and <sup>15</sup>N nuclear magnetic resonance spectroscopy and with electron spray ionization time-of-flight mass spectrometry. Furthermore, time-resolved electron paramagnetic resonance spectroscopy and time-resolved ultraviolet-visible spectroscopy were carried out. Thus, radical intermediates were detected, which were consumed with reaction time. Finally, we postulate a reaction mechanism for the S<sub>4</sub>N<sub>4</sub>-IL- and S<sub>4</sub><sup>15</sup>N<sub>4</sub>-IL systems and compare this with the respective data for the (SN)<sub><i>x</i></sub> -IL- and (S<sup>15</sup>N)<sub><i>x</i></sub>-IL-systems.</p>\",\"PeriodicalId\":60,\"journal\":{\"name\":\"The Journal of Physical Chemistry B\",\"volume\":\"129 16\",\"pages\":\"4063-4077\"},\"PeriodicalIF\":2.9000,\"publicationDate\":\"2025-04-24\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12035862/pdf/\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"The Journal of Physical Chemistry B\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.jpcb.5c00294\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"2025/4/10 0:00:00\",\"PubModel\":\"Epub\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"The Journal of Physical Chemistry B","FirstCategoryId":"1","ListUrlMain":"https://doi.org/10.1021/acs.jpcb.5c00294","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2025/4/10 0:00:00","PubModel":"Epub","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
摘要
本文主要研究了聚氮化硫(SN)x, (S15N)x与离子液体(IL) 1-乙基-3-甲基咪唑醋酸盐[EMIm][OAc]的反应机理。我们将此与IL与S4N4或其15n标记形式S415N4(合成(SN)x和(S15N)x的前体)的反应进行比较。通过柱层析纯化S4N4-IL-和S415N4-IL体系后,利用1H、13C和15N核磁共振波谱和电子喷雾电离飞行时间质谱对反应产物进行了表征。此外,还进行了时间分辨电子顺磁共振波谱和时间分辨紫外可见波谱。因此,检测到自由基中间体,这些中间体随着反应时间的推移而消耗。最后,我们假设了S4N4-IL-和S415N4-IL体系的反应机制,并将其与(SN)x - il -和(S15N)x- il体系的相应数据进行了比较。
Nuclear Magnetic Resonance- and Electron Paramagnetic Resonance Spectroscopic Characterization of S4N4 and (SN)x Dissolved in [EMIm][OAc].
This work focuses on the reaction mechanism of poly(sulfur nitride) ((SN)x, (S15N)x), with the ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate [EMIm][OAc]. We compare this with the reaction of the IL with S4N4 or its 15N-labeled form S415N4, a precursor for the synthesis of (SN)x and (S15N)x. After purification of the S4N4-IL- and S415N4-IL systems via column chromatography, we characterized the reaction products with 1H, 13C, and 15N nuclear magnetic resonance spectroscopy and with electron spray ionization time-of-flight mass spectrometry. Furthermore, time-resolved electron paramagnetic resonance spectroscopy and time-resolved ultraviolet-visible spectroscopy were carried out. Thus, radical intermediates were detected, which were consumed with reaction time. Finally, we postulate a reaction mechanism for the S4N4-IL- and S415N4-IL systems and compare this with the respective data for the (SN)x -IL- and (S15N)x-IL-systems.
期刊介绍:
An essential criterion for acceptance of research articles in the journal is that they provide new physical insight. Please refer to the New Physical Insights virtual issue on what constitutes new physical insight. Manuscripts that are essentially reporting data or applications of data are, in general, not suitable for publication in JPC B.