Recombination of Lophyl Radicals in Pyrrolidinium-Based Ionic Liquids
The recombination of photolytically generated lophyl radicals has been investigated by UV/Vis spectroscopy in 1‐alkyl‐1‐methylpyrrolidinium bis(trifluoromethylsulfonyl)imides (NTf2) in comparison with 1‐butyl‐3‐methylimidazolium NTf2, dimethyl sulfoxide, and triacetin. The 1‐alkyl‐1‐methylpyrrolidin...
Gespeichert in:
| Veröffentlicht in: | Chemphyschem 2013-06, Vol.14 (9), p.1899-1908 |
|---|---|
| Hauptverfasser: | , , , |
| Format: | Artikel |
| Sprache: | eng |
| Schlagworte: | |
| Online-Zugang: | Volltext |
| Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
| container_end_page | 1908 |
|---|---|
| container_issue | 9 |
| container_start_page | 1899 |
| container_title | Chemphyschem |
| container_volume | 14 |
| creator | Berdzinski, Stefan Horst, Joachim Straßburg, Petra Strehmel, Veronika |
| description | The recombination of photolytically generated lophyl radicals has been investigated by UV/Vis spectroscopy in 1‐alkyl‐1‐methylpyrrolidinium bis(trifluoromethylsulfonyl)imides (NTf2) in comparison with 1‐butyl‐3‐methylimidazolium NTf2, dimethyl sulfoxide, and triacetin. The 1‐alkyl‐1‐methylpyrrolidinium‐based ionic liquids contain an alkyl substituent varying between butyl and decyl groups. Optically pure ionic liquids are used in these studies. Temperature‐dependent investigation of lophyl radical recombination shows an increase in the radical recombination rate with increasing temperature in each solvent, which is caused by decreasing viscosity with increasing temperature. Furthermore, the viscosity of the 1‐alkyl‐1‐methylpyrrolidinium NTf2 increases nearly linearly within the row of these ionic liquids. In contrast, the recombination of the photolytically generated lophyl radicals is significantly faster in the ionic liquids than in the traditional organic solvents under investigation. Moreover, the recombination rate increases with the length of the alkyl chain bound at the cation of the ionic liquid at a given temperature. This may be caused by an increase in the extent of lophyl radical recombination within the solvent cage. Solvent cage effects dominate in the case of lophyl radical recombination in ionic liquids bearing a long alkyl chain or if the temperature is near the melting temperature of the ionic liquid. The positive value of the activation entropy supports this hypothesis. The results obtained are important for discussion of bimolecular radical reactions in ionic liquids.
Rate increases: Long alkyl chains bound at the cation of 1‐alkyl‐1‐methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ionic liquids change the steric requirements on the transition state of the bimolecular lophyl radical recombination reaction (see picture). Recombination of the photolytically generated radicals is faster in the ionic liquids than in traditional organic solvents. |
| doi_str_mv | 10.1002/cphc.201300098 |
| format | Article |
| fullrecord | <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_miscellaneous_1367886291</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>2995409011</sourcerecordid><originalsourceid>FETCH-LOGICAL-c5078-f830b8b265ffbc21d0dcfaee49082b76c8cdac1e21d7cf261634e6c9aceefc53</originalsourceid><addsrcrecordid>eNqF0M1P2zAYB2ALDY2P7cpxijRN4pLij8R2jqyjFClsqELa0XLe2MKQxMVuNPrfY2jp0C47-ZX8vB_6IXRC8IRgTM9geQcTignDGFdyDx2SglW54AX5sK0LysoDdBTjfSISC_IRHVDGi4pjeYguFgZ837hBr5wfMm-z2i_v1l220K0D3cXMDdnNOgTfudYNbuzz7zqaNrvyg4Osdo-ja-MntG-TNZ-37zG6nV3cTud5_evyanpe51BiIXMrGW5kQ3lpbQOUtLgFq40pKixpIzhIaDUQk34EWMoJZ4XhUGkwxkLJjtHpZuwy-MfRxJXqXQTTdXowfoyKMC6k5LQiiX79h977MQzpuFdVcEYFTWqyURB8jMFYtQyu12GtCFYv-aqXfNUu39TwZTt2bHrT7vhboAl82wIdU3w26AFc_OvS5lJylly1cX9cZ9b_WaumN_Pp-yPyTa-LK_O069XhQXHBRKl-_7xUi1kpZtc_ajVnz_tDovM</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>1367463272</pqid></control><display><type>article</type><title>Recombination of Lophyl Radicals in Pyrrolidinium-Based Ionic Liquids</title><source>Wiley Online Library Journals Frontfile Complete</source><creator>Berdzinski, Stefan ; Horst, Joachim ; Straßburg, Petra ; Strehmel, Veronika</creator><creatorcontrib>Berdzinski, Stefan ; Horst, Joachim ; Straßburg, Petra ; Strehmel, Veronika</creatorcontrib><description>The recombination of photolytically generated lophyl radicals has been investigated by UV/Vis spectroscopy in 1‐alkyl‐1‐methylpyrrolidinium bis(trifluoromethylsulfonyl)imides (NTf2) in comparison with 1‐butyl‐3‐methylimidazolium NTf2, dimethyl sulfoxide, and triacetin. The 1‐alkyl‐1‐methylpyrrolidinium‐based ionic liquids contain an alkyl substituent varying between butyl and decyl groups. Optically pure ionic liquids are used in these studies. Temperature‐dependent investigation of lophyl radical recombination shows an increase in the radical recombination rate with increasing temperature in each solvent, which is caused by decreasing viscosity with increasing temperature. Furthermore, the viscosity of the 1‐alkyl‐1‐methylpyrrolidinium NTf2 increases nearly linearly within the row of these ionic liquids. In contrast, the recombination of the photolytically generated lophyl radicals is significantly faster in the ionic liquids than in the traditional organic solvents under investigation. Moreover, the recombination rate increases with the length of the alkyl chain bound at the cation of the ionic liquid at a given temperature. This may be caused by an increase in the extent of lophyl radical recombination within the solvent cage. Solvent cage effects dominate in the case of lophyl radical recombination in ionic liquids bearing a long alkyl chain or if the temperature is near the melting temperature of the ionic liquid. The positive value of the activation entropy supports this hypothesis. The results obtained are important for discussion of bimolecular radical reactions in ionic liquids.
Rate increases: Long alkyl chains bound at the cation of 1‐alkyl‐1‐methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ionic liquids change the steric requirements on the transition state of the bimolecular lophyl radical recombination reaction (see picture). Recombination of the photolytically generated radicals is faster in the ionic liquids than in traditional organic solvents.</description><identifier>ISSN: 1439-4235</identifier><identifier>EISSN: 1439-7641</identifier><identifier>DOI: 10.1002/cphc.201300098</identifier><identifier>PMID: 23649608</identifier><language>eng</language><publisher>Weinheim: WILEY-VCH Verlag</publisher><subject>Chemistry ; Exact sciences and technology ; General and physical chemistry ; ionic liquids ; Ions ; Liquids ; lophyl radicals ; Photochemistry ; photolysis ; Physical chemistry of induced reactions (with radiations, particles and ultrasonics) ; radical reactions ; recombination ; Solvents</subject><ispartof>Chemphyschem, 2013-06, Vol.14 (9), p.1899-1908</ispartof><rights>Copyright © 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim</rights><rights>2014 INIST-CNRS</rights><rights>Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.</rights><rights>Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c5078-f830b8b265ffbc21d0dcfaee49082b76c8cdac1e21d7cf261634e6c9aceefc53</citedby><cites>FETCH-LOGICAL-c5078-f830b8b265ffbc21d0dcfaee49082b76c8cdac1e21d7cf261634e6c9aceefc53</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Fcphc.201300098$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fcphc.201300098$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,776,780,1411,27903,27904,45553,45554</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=27465863$$DView record in Pascal Francis$$Hfree_for_read</backlink><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/23649608$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Berdzinski, Stefan</creatorcontrib><creatorcontrib>Horst, Joachim</creatorcontrib><creatorcontrib>Straßburg, Petra</creatorcontrib><creatorcontrib>Strehmel, Veronika</creatorcontrib><title>Recombination of Lophyl Radicals in Pyrrolidinium-Based Ionic Liquids</title><title>Chemphyschem</title><addtitle>ChemPhysChem</addtitle><description>The recombination of photolytically generated lophyl radicals has been investigated by UV/Vis spectroscopy in 1‐alkyl‐1‐methylpyrrolidinium bis(trifluoromethylsulfonyl)imides (NTf2) in comparison with 1‐butyl‐3‐methylimidazolium NTf2, dimethyl sulfoxide, and triacetin. The 1‐alkyl‐1‐methylpyrrolidinium‐based ionic liquids contain an alkyl substituent varying between butyl and decyl groups. Optically pure ionic liquids are used in these studies. Temperature‐dependent investigation of lophyl radical recombination shows an increase in the radical recombination rate with increasing temperature in each solvent, which is caused by decreasing viscosity with increasing temperature. Furthermore, the viscosity of the 1‐alkyl‐1‐methylpyrrolidinium NTf2 increases nearly linearly within the row of these ionic liquids. In contrast, the recombination of the photolytically generated lophyl radicals is significantly faster in the ionic liquids than in the traditional organic solvents under investigation. Moreover, the recombination rate increases with the length of the alkyl chain bound at the cation of the ionic liquid at a given temperature. This may be caused by an increase in the extent of lophyl radical recombination within the solvent cage. Solvent cage effects dominate in the case of lophyl radical recombination in ionic liquids bearing a long alkyl chain or if the temperature is near the melting temperature of the ionic liquid. The positive value of the activation entropy supports this hypothesis. The results obtained are important for discussion of bimolecular radical reactions in ionic liquids.
Rate increases: Long alkyl chains bound at the cation of 1‐alkyl‐1‐methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ionic liquids change the steric requirements on the transition state of the bimolecular lophyl radical recombination reaction (see picture). Recombination of the photolytically generated radicals is faster in the ionic liquids than in traditional organic solvents.</description><subject>Chemistry</subject><subject>Exact sciences and technology</subject><subject>General and physical chemistry</subject><subject>ionic liquids</subject><subject>Ions</subject><subject>Liquids</subject><subject>lophyl radicals</subject><subject>Photochemistry</subject><subject>photolysis</subject><subject>Physical chemistry of induced reactions (with radiations, particles and ultrasonics)</subject><subject>radical reactions</subject><subject>recombination</subject><subject>Solvents</subject><issn>1439-4235</issn><issn>1439-7641</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2013</creationdate><recordtype>article</recordtype><recordid>eNqF0M1P2zAYB2ALDY2P7cpxijRN4pLij8R2jqyjFClsqELa0XLe2MKQxMVuNPrfY2jp0C47-ZX8vB_6IXRC8IRgTM9geQcTignDGFdyDx2SglW54AX5sK0LysoDdBTjfSISC_IRHVDGi4pjeYguFgZ837hBr5wfMm-z2i_v1l220K0D3cXMDdnNOgTfudYNbuzz7zqaNrvyg4Osdo-ja-MntG-TNZ-37zG6nV3cTud5_evyanpe51BiIXMrGW5kQ3lpbQOUtLgFq40pKixpIzhIaDUQk34EWMoJZ4XhUGkwxkLJjtHpZuwy-MfRxJXqXQTTdXowfoyKMC6k5LQiiX79h977MQzpuFdVcEYFTWqyURB8jMFYtQyu12GtCFYv-aqXfNUu39TwZTt2bHrT7vhboAl82wIdU3w26AFc_OvS5lJylly1cX9cZ9b_WaumN_Pp-yPyTa-LK_O069XhQXHBRKl-_7xUi1kpZtc_ajVnz_tDovM</recordid><startdate>20130624</startdate><enddate>20130624</enddate><creator>Berdzinski, Stefan</creator><creator>Horst, Joachim</creator><creator>Straßburg, Petra</creator><creator>Strehmel, Veronika</creator><general>WILEY-VCH Verlag</general><general>WILEY‐VCH Verlag</general><general>Wiley</general><general>Wiley Subscription Services, Inc</general><scope>BSCLL</scope><scope>IQODW</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>K9.</scope><scope>7X8</scope></search><sort><creationdate>20130624</creationdate><title>Recombination of Lophyl Radicals in Pyrrolidinium-Based Ionic Liquids</title><author>Berdzinski, Stefan ; Horst, Joachim ; Straßburg, Petra ; Strehmel, Veronika</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c5078-f830b8b265ffbc21d0dcfaee49082b76c8cdac1e21d7cf261634e6c9aceefc53</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2013</creationdate><topic>Chemistry</topic><topic>Exact sciences and technology</topic><topic>General and physical chemistry</topic><topic>ionic liquids</topic><topic>Ions</topic><topic>Liquids</topic><topic>lophyl radicals</topic><topic>Photochemistry</topic><topic>photolysis</topic><topic>Physical chemistry of induced reactions (with radiations, particles and ultrasonics)</topic><topic>radical reactions</topic><topic>recombination</topic><topic>Solvents</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Berdzinski, Stefan</creatorcontrib><creatorcontrib>Horst, Joachim</creatorcontrib><creatorcontrib>Straßburg, Petra</creatorcontrib><creatorcontrib>Strehmel, Veronika</creatorcontrib><collection>Istex</collection><collection>Pascal-Francis</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>MEDLINE - Academic</collection><jtitle>Chemphyschem</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Berdzinski, Stefan</au><au>Horst, Joachim</au><au>Straßburg, Petra</au><au>Strehmel, Veronika</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Recombination of Lophyl Radicals in Pyrrolidinium-Based Ionic Liquids</atitle><jtitle>Chemphyschem</jtitle><addtitle>ChemPhysChem</addtitle><date>2013-06-24</date><risdate>2013</risdate><volume>14</volume><issue>9</issue><spage>1899</spage><epage>1908</epage><pages>1899-1908</pages><issn>1439-4235</issn><eissn>1439-7641</eissn><abstract>The recombination of photolytically generated lophyl radicals has been investigated by UV/Vis spectroscopy in 1‐alkyl‐1‐methylpyrrolidinium bis(trifluoromethylsulfonyl)imides (NTf2) in comparison with 1‐butyl‐3‐methylimidazolium NTf2, dimethyl sulfoxide, and triacetin. The 1‐alkyl‐1‐methylpyrrolidinium‐based ionic liquids contain an alkyl substituent varying between butyl and decyl groups. Optically pure ionic liquids are used in these studies. Temperature‐dependent investigation of lophyl radical recombination shows an increase in the radical recombination rate with increasing temperature in each solvent, which is caused by decreasing viscosity with increasing temperature. Furthermore, the viscosity of the 1‐alkyl‐1‐methylpyrrolidinium NTf2 increases nearly linearly within the row of these ionic liquids. In contrast, the recombination of the photolytically generated lophyl radicals is significantly faster in the ionic liquids than in the traditional organic solvents under investigation. Moreover, the recombination rate increases with the length of the alkyl chain bound at the cation of the ionic liquid at a given temperature. This may be caused by an increase in the extent of lophyl radical recombination within the solvent cage. Solvent cage effects dominate in the case of lophyl radical recombination in ionic liquids bearing a long alkyl chain or if the temperature is near the melting temperature of the ionic liquid. The positive value of the activation entropy supports this hypothesis. The results obtained are important for discussion of bimolecular radical reactions in ionic liquids.
Rate increases: Long alkyl chains bound at the cation of 1‐alkyl‐1‐methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ionic liquids change the steric requirements on the transition state of the bimolecular lophyl radical recombination reaction (see picture). Recombination of the photolytically generated radicals is faster in the ionic liquids than in traditional organic solvents.</abstract><cop>Weinheim</cop><pub>WILEY-VCH Verlag</pub><pmid>23649608</pmid><doi>10.1002/cphc.201300098</doi><tpages>10</tpages></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 1439-4235 |
| ispartof | Chemphyschem, 2013-06, Vol.14 (9), p.1899-1908 |
| issn | 1439-4235 1439-7641 |
| language | eng |
| recordid | cdi_proquest_miscellaneous_1367886291 |
| source | Wiley Online Library Journals Frontfile Complete |
| subjects | Chemistry Exact sciences and technology General and physical chemistry ionic liquids Ions Liquids lophyl radicals Photochemistry photolysis Physical chemistry of induced reactions (with radiations, particles and ultrasonics) radical reactions recombination Solvents |
| title | Recombination of Lophyl Radicals in Pyrrolidinium-Based Ionic Liquids |
| url | https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-01-26T12%3A47%3A29IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_cross&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Recombination%20of%20Lophyl%20Radicals%20in%20Pyrrolidinium-Based%20Ionic%20Liquids&rft.jtitle=Chemphyschem&rft.au=Berdzinski,%20Stefan&rft.date=2013-06-24&rft.volume=14&rft.issue=9&rft.spage=1899&rft.epage=1908&rft.pages=1899-1908&rft.issn=1439-4235&rft.eissn=1439-7641&rft_id=info:doi/10.1002/cphc.201300098&rft_dat=%3Cproquest_cross%3E2995409011%3C/proquest_cross%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_pqid=1367463272&rft_id=info:pmid/23649608&rfr_iscdi=true |