Marina Kinzelmann, Nina Fröhlich, Alexander Vogel, Milan Kivala, Thomas Drewello
{"title":"π-扩展三苯胺和 N-杂三庚烯支架的串联质谱分析:辐射阳离子与银(I)加合物。","authors":"Marina Kinzelmann, Nina Fröhlich, Alexander Vogel, Milan Kivala, Thomas Drewello","doi":"10.1002/jms.5079","DOIUrl":null,"url":null,"abstract":"<p>Triphenylamine (TPA) and <i>N</i>-heterotriangulene (<i>N</i>-HTA) scaffolds with up to three oligophenyl extensions are investigated by electrospray ionization (tandem) mass spectrometry (ESI-[MS/]MS). Due to their low oxidation potentials, all molecules readily form radical cations in the electrospray process. The energy-resolved collision-induced dissociation behaviour of the molecular ions is contrasted to that of the silver(I) adducts. Complexation with Ag(I) leads to the expected [1:1] and [2:1] complexes (MAg<sup>+</sup> and M<sub>2</sub>Ag<sup>+</sup>); however, even [1:2] complexes (MAg<sub>2</sub><sup>2+</sup>) can be detected for molecules with two and three large π-expansions to allow stabilization of two charges. The TPA scaffolds decompose only at high collision energies through the loss of peripheral <i>tert</i>-butyl groups. A general mechanism for this is proposed commencing with a methyl loss and followed by the release of <i>iso</i>butene and butyl radical moieties. The <i>N</i>-HTA-based scaffolds are considerably less stable and molecular ions fragment at low collision energies. This is caused by the facile loss of methyl radicals from the dimethylmethylene-bridged triangulene core. In contrast, complexation with Ag<sup>+</sup> leads to a dramatic stabilization. Most interestingly, dissociation eventually proceeds via the loss of neutral AgCH<sub>3</sub>, which is indicative of strong bidentate, tweezer-like bonding of Ag<sup>+</sup> to the molecules.</p>","PeriodicalId":16178,"journal":{"name":"Journal of Mass Spectrometry","volume":"59 9","pages":""},"PeriodicalIF":1.9000,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/jms.5079","citationCount":"0","resultStr":"{\"title\":\"Tandem mass spectrometry of π-expanded triphenylamine and N-heterotriangulene scaffolds: Radical cation versus silver(I) adduct\",\"authors\":\"Marina Kinzelmann, Nina Fröhlich, Alexander Vogel, Milan Kivala, Thomas Drewello\",\"doi\":\"10.1002/jms.5079\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>Triphenylamine (TPA) and <i>N</i>-heterotriangulene (<i>N</i>-HTA) scaffolds with up to three oligophenyl extensions are investigated by electrospray ionization (tandem) mass spectrometry (ESI-[MS/]MS). Due to their low oxidation potentials, all molecules readily form radical cations in the electrospray process. The energy-resolved collision-induced dissociation behaviour of the molecular ions is contrasted to that of the silver(I) adducts. Complexation with Ag(I) leads to the expected [1:1] and [2:1] complexes (MAg<sup>+</sup> and M<sub>2</sub>Ag<sup>+</sup>); however, even [1:2] complexes (MAg<sub>2</sub><sup>2+</sup>) can be detected for molecules with two and three large π-expansions to allow stabilization of two charges. The TPA scaffolds decompose only at high collision energies through the loss of peripheral <i>tert</i>-butyl groups. A general mechanism for this is proposed commencing with a methyl loss and followed by the release of <i>iso</i>butene and butyl radical moieties. The <i>N</i>-HTA-based scaffolds are considerably less stable and molecular ions fragment at low collision energies. This is caused by the facile loss of methyl radicals from the dimethylmethylene-bridged triangulene core. In contrast, complexation with Ag<sup>+</sup> leads to a dramatic stabilization. Most interestingly, dissociation eventually proceeds via the loss of neutral AgCH<sub>3</sub>, which is indicative of strong bidentate, tweezer-like bonding of Ag<sup>+</sup> to the molecules.</p>\",\"PeriodicalId\":16178,\"journal\":{\"name\":\"Journal of Mass Spectrometry\",\"volume\":\"59 9\",\"pages\":\"\"},\"PeriodicalIF\":1.9000,\"publicationDate\":\"2024-08-12\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://onlinelibrary.wiley.com/doi/epdf/10.1002/jms.5079\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Mass Spectrometry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://onlinelibrary.wiley.com/doi/10.1002/jms.5079\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"BIOCHEMICAL RESEARCH METHODS\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Mass Spectrometry","FirstCategoryId":"92","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/jms.5079","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"BIOCHEMICAL RESEARCH METHODS","Score":null,"Total":0}
Tandem mass spectrometry of π-expanded triphenylamine and N-heterotriangulene scaffolds: Radical cation versus silver(I) adduct
Triphenylamine (TPA) and N-heterotriangulene (N-HTA) scaffolds with up to three oligophenyl extensions are investigated by electrospray ionization (tandem) mass spectrometry (ESI-[MS/]MS). Due to their low oxidation potentials, all molecules readily form radical cations in the electrospray process. The energy-resolved collision-induced dissociation behaviour of the molecular ions is contrasted to that of the silver(I) adducts. Complexation with Ag(I) leads to the expected [1:1] and [2:1] complexes (MAg+ and M2Ag+); however, even [1:2] complexes (MAg22+) can be detected for molecules with two and three large π-expansions to allow stabilization of two charges. The TPA scaffolds decompose only at high collision energies through the loss of peripheral tert-butyl groups. A general mechanism for this is proposed commencing with a methyl loss and followed by the release of isobutene and butyl radical moieties. The N-HTA-based scaffolds are considerably less stable and molecular ions fragment at low collision energies. This is caused by the facile loss of methyl radicals from the dimethylmethylene-bridged triangulene core. In contrast, complexation with Ag+ leads to a dramatic stabilization. Most interestingly, dissociation eventually proceeds via the loss of neutral AgCH3, which is indicative of strong bidentate, tweezer-like bonding of Ag+ to the molecules.
期刊介绍:
The Journal of Mass Spectrometry publishes papers on a broad range of topics of interest to scientists working in both fundamental and applied areas involving the study of gaseous ions.
The aim of JMS is to serve the scientific community with information provided and arranged to help senior investigators to better stay abreast of new discoveries and studies in their own field, to make them aware of events and developments in associated fields, and to provide students and newcomers the basic tools with which to learn fundamental and applied aspects of mass spectrometry.