Photolysis of a High‐Spin Azidoiron(III) Complex Studied by Time‐Resolved Fourier‐Transform Infrared Spectroscopy
The laser‐flash photolysis of the high‐spin azidoiron(III) complex [FeIII(Me3Cyclam‐ac)(N3)]PF6 ([1]PF6) in liquid acetonitrile solution at room temperature was explored by time‐resolved Fourier‐transform infrared spectroscopy. Excitation of [1] at 480 and 266 nm induced a photoreduction of the meta...
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| Veröffentlicht in: | Chemistry : a European journal 2017-05, Vol.23 (28), p.6746-6751 |
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| creator | Torres‐Alacan, Joel Vöhringer, Peter |
| description | The laser‐flash photolysis of the high‐spin azidoiron(III) complex [FeIII(Me3Cyclam‐ac)(N3)]PF6 ([1]PF6) in liquid acetonitrile solution at room temperature was explored by time‐resolved Fourier‐transform infrared spectroscopy. Excitation of [1] at 480 and 266 nm induced a photoreduction of the metal center and generated [FeII(Me3Cyclam‐ac)(NCCH3)]+ ([2]) and azidyl radicals. Both photoproducts were detected independently through scavenging experiments. The metal‐containing fragment was quenched with carbon monoxide to generate an iron(II) carbonyl complex, whereas the nitrogen‐containing fragment was quenched with iodide to form azide anions. In the presence of N3−, the photoreduction created the elusive hexanitrogen radical anion N6.− as a transient byproduct.
A closer look at photolysis: Time‐resolved infrared spectroscopy is used to explore the liquid‐phase photochemistry of the high‐spin ferric azide complex [FeIII(Me3Cyclam‐ac)(N3)]PF6. Excitation of the complex at 480 and 266 nm induced a photoreduction of the metal center and generated [FeII(Me3Cyclam‐ac)(NCCH3)]+ and azidyl radicals. |
| doi_str_mv | 10.1002/chem.201700960 |
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A closer look at photolysis: Time‐resolved infrared spectroscopy is used to explore the liquid‐phase photochemistry of the high‐spin ferric azide complex [FeIII(Me3Cyclam‐ac)(N3)]PF6. Excitation of the complex at 480 and 266 nm induced a photoreduction of the metal center and generated [FeII(Me3Cyclam‐ac)(NCCH3)]+ and azidyl radicals.</description><identifier>ISSN: 0947-6539</identifier><identifier>EISSN: 1521-3765</identifier><identifier>DOI: 10.1002/chem.201700960</identifier><identifier>PMID: 28370514</identifier><language>eng</language><publisher>Germany: Wiley Subscription Services, Inc</publisher><subject>Acetonitrile ; Anions ; Carbon monoxide ; Carbonyl compounds ; Carbonyls ; Chemistry ; Excitation spectra ; Flash photolysis ; Fourier transforms ; high-valent iron ; Infrared lasers ; Infrared spectroscopy ; Iodides ; photochemistry ; Photolysis ; Photoreduction ; Quenching ; Room temperature ; Scavenging ; Spectrum analysis ; time-resolved ; transition-metal complexes</subject><ispartof>Chemistry : a European journal, 2017-05, Vol.23 (28), p.6746-6751</ispartof><rights>2017 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim</rights><rights>2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.</rights><rights>2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c4100-99978f00c2e5fde615f590052bc727207ba3463ba32babb092265983df6545b13</citedby><cites>FETCH-LOGICAL-c4100-99978f00c2e5fde615f590052bc727207ba3463ba32babb092265983df6545b13</cites><orcidid>0000-0003-3098-0428</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Fchem.201700960$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fchem.201700960$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,780,784,1417,27924,27925,45574,45575</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/28370514$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Torres‐Alacan, Joel</creatorcontrib><creatorcontrib>Vöhringer, Peter</creatorcontrib><title>Photolysis of a High‐Spin Azidoiron(III) Complex Studied by Time‐Resolved Fourier‐Transform Infrared Spectroscopy</title><title>Chemistry : a European journal</title><addtitle>Chemistry</addtitle><description>The laser‐flash photolysis of the high‐spin azidoiron(III) complex [FeIII(Me3Cyclam‐ac)(N3)]PF6 ([1]PF6) in liquid acetonitrile solution at room temperature was explored by time‐resolved Fourier‐transform infrared spectroscopy. Excitation of [1] at 480 and 266 nm induced a photoreduction of the metal center and generated [FeII(Me3Cyclam‐ac)(NCCH3)]+ ([2]) and azidyl radicals. Both photoproducts were detected independently through scavenging experiments. The metal‐containing fragment was quenched with carbon monoxide to generate an iron(II) carbonyl complex, whereas the nitrogen‐containing fragment was quenched with iodide to form azide anions. In the presence of N3−, the photoreduction created the elusive hexanitrogen radical anion N6.− as a transient byproduct.
A closer look at photolysis: Time‐resolved infrared spectroscopy is used to explore the liquid‐phase photochemistry of the high‐spin ferric azide complex [FeIII(Me3Cyclam‐ac)(N3)]PF6. Excitation of the complex at 480 and 266 nm induced a photoreduction of the metal center and generated [FeII(Me3Cyclam‐ac)(NCCH3)]+ and azidyl radicals.</description><subject>Acetonitrile</subject><subject>Anions</subject><subject>Carbon monoxide</subject><subject>Carbonyl compounds</subject><subject>Carbonyls</subject><subject>Chemistry</subject><subject>Excitation spectra</subject><subject>Flash photolysis</subject><subject>Fourier transforms</subject><subject>high-valent iron</subject><subject>Infrared lasers</subject><subject>Infrared spectroscopy</subject><subject>Iodides</subject><subject>photochemistry</subject><subject>Photolysis</subject><subject>Photoreduction</subject><subject>Quenching</subject><subject>Room temperature</subject><subject>Scavenging</subject><subject>Spectrum analysis</subject><subject>time-resolved</subject><subject>transition-metal complexes</subject><issn>0947-6539</issn><issn>1521-3765</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2017</creationdate><recordtype>article</recordtype><recordid>eNqFkc9O3DAQxq2KCrYL1x6RJS5wyHZsx058RCtgI4FadZdzlD921yiJU3sDhFMfgWfkSfBqKUi99DIjzfzm03z6EPpKYEYA6LdqrdoZBZIASAGf0IRwSiKWCL6HJiDjJBKcyQP0xfs72DKM7aMDmrIEOIkn6OHH2m5sM3rjsdW4wAvza_3y53nZmw6fP5naGme70yzLzvDctn2jHvFyM9RG1bgc8cq0KtA_lbfNfRhd2sEZ5cJo5YrOa-tanHXaFS4sl72qNs76yvbjIfqsi8aro7c-RbeXF6v5Irr-fpXNz6-jKg7-IillkmqAiiquayUI11wCcFpWCU0oJGXBYsFCpWVRliApFVymrNaCx7wkbIpOd7q9s78H5Td5a3ylmqbolB18TtI0JkKycDNFJ_-gd8FNF74LVPhDilTSQM12VBWceKd03jvTFm7MCeTbSPJtJPl7JOHg-E12KFtVv-N_MwiA3AEPplHjf-Ty-eLi5kP8FbRFmmQ</recordid><startdate>20170517</startdate><enddate>20170517</enddate><creator>Torres‐Alacan, Joel</creator><creator>Vöhringer, Peter</creator><general>Wiley Subscription Services, Inc</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>K9.</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0003-3098-0428</orcidid></search><sort><creationdate>20170517</creationdate><title>Photolysis of a High‐Spin Azidoiron(III) Complex Studied by Time‐Resolved Fourier‐Transform Infrared Spectroscopy</title><author>Torres‐Alacan, Joel ; Vöhringer, Peter</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c4100-99978f00c2e5fde615f590052bc727207ba3463ba32babb092265983df6545b13</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2017</creationdate><topic>Acetonitrile</topic><topic>Anions</topic><topic>Carbon monoxide</topic><topic>Carbonyl compounds</topic><topic>Carbonyls</topic><topic>Chemistry</topic><topic>Excitation spectra</topic><topic>Flash photolysis</topic><topic>Fourier transforms</topic><topic>high-valent iron</topic><topic>Infrared lasers</topic><topic>Infrared spectroscopy</topic><topic>Iodides</topic><topic>photochemistry</topic><topic>Photolysis</topic><topic>Photoreduction</topic><topic>Quenching</topic><topic>Room temperature</topic><topic>Scavenging</topic><topic>Spectrum analysis</topic><topic>time-resolved</topic><topic>transition-metal complexes</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Torres‐Alacan, Joel</creatorcontrib><creatorcontrib>Vöhringer, Peter</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>MEDLINE - Academic</collection><jtitle>Chemistry : a European journal</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Torres‐Alacan, Joel</au><au>Vöhringer, Peter</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Photolysis of a High‐Spin Azidoiron(III) Complex Studied by Time‐Resolved Fourier‐Transform Infrared Spectroscopy</atitle><jtitle>Chemistry : a European journal</jtitle><addtitle>Chemistry</addtitle><date>2017-05-17</date><risdate>2017</risdate><volume>23</volume><issue>28</issue><spage>6746</spage><epage>6751</epage><pages>6746-6751</pages><issn>0947-6539</issn><eissn>1521-3765</eissn><abstract>The laser‐flash photolysis of the high‐spin azidoiron(III) complex [FeIII(Me3Cyclam‐ac)(N3)]PF6 ([1]PF6) in liquid acetonitrile solution at room temperature was explored by time‐resolved Fourier‐transform infrared spectroscopy. Excitation of [1] at 480 and 266 nm induced a photoreduction of the metal center and generated [FeII(Me3Cyclam‐ac)(NCCH3)]+ ([2]) and azidyl radicals. Both photoproducts were detected independently through scavenging experiments. The metal‐containing fragment was quenched with carbon monoxide to generate an iron(II) carbonyl complex, whereas the nitrogen‐containing fragment was quenched with iodide to form azide anions. In the presence of N3−, the photoreduction created the elusive hexanitrogen radical anion N6.− as a transient byproduct.
A closer look at photolysis: Time‐resolved infrared spectroscopy is used to explore the liquid‐phase photochemistry of the high‐spin ferric azide complex [FeIII(Me3Cyclam‐ac)(N3)]PF6. Excitation of the complex at 480 and 266 nm induced a photoreduction of the metal center and generated [FeII(Me3Cyclam‐ac)(NCCH3)]+ and azidyl radicals.</abstract><cop>Germany</cop><pub>Wiley Subscription Services, Inc</pub><pmid>28370514</pmid><doi>10.1002/chem.201700960</doi><tpages>6</tpages><orcidid>https://orcid.org/0000-0003-3098-0428</orcidid></addata></record> |
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| subjects | Acetonitrile Anions Carbon monoxide Carbonyl compounds Carbonyls Chemistry Excitation spectra Flash photolysis Fourier transforms high-valent iron Infrared lasers Infrared spectroscopy Iodides photochemistry Photolysis Photoreduction Quenching Room temperature Scavenging Spectrum analysis time-resolved transition-metal complexes |
| title | Photolysis of a High‐Spin Azidoiron(III) Complex Studied by Time‐Resolved Fourier‐Transform Infrared Spectroscopy |
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