Time-Resolved Electron Paramagnetic Resonance Study of Rhodium(III) Corrole Excited States
Photoexcited states of three Rh(III) 5,10,15-tris(pentafluorophenyl)corroles coordinated by different axial ligands; namely, triphenylphosphine P(C6H5)3 group (1), pyridine C6H5N group (2), and two pyridine groups (3) were studied by X- and Q-band time-resolved electron paramagnetic resonance (TREPR...
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Veröffentlicht in: | The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2010-02, Vol.114 (5), p.2059-2072 |
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creator | Wagnert, Linn Berg, Alexander Saltsman, Irena Gross, Zeev Rozenshtein, Vladimir |
description | Photoexcited states of three Rh(III) 5,10,15-tris(pentafluorophenyl)corroles coordinated by different axial ligands; namely, triphenylphosphine P(C6H5)3 group (1), pyridine C6H5N group (2), and two pyridine groups (3) were studied by X- and Q-band time-resolved electron paramagnetic resonance (TREPR) in frozen toluene and liquid crystal E-7. Transient mutations were utilized to identify multiplicity of the detected paramagnetic species. The spectra of 1 and 2 were assigned to triplet (3ππ*) states, while contributions of triplet (3dd and charge transfer 3CT) and quintet (5dd) states were revealed in the spectrum of 3. The results are interpreted in terms of a peculiar nature of transition metal complexes with the unfilled d-shell, where close lying electronic states of different multiplicities may be mixed through configurational, spin−orbit, and vibronic coupling. From the EPR spectra, the spin−orbit coupling constant was estimated to be about 25 cm−1. It is shown that different axial ligation of complexes shifts the relative energy of the excited states and, consequently, leads to population of different states. Plausible explanations of the effects governing unusual spectral and dynamic parameters of the photoexcited Rh corrole complexes are presented. |
doi_str_mv | 10.1021/jp909967b |
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Transient mutations were utilized to identify multiplicity of the detected paramagnetic species. The spectra of 1 and 2 were assigned to triplet (3ππ*) states, while contributions of triplet (3dd and charge transfer 3CT) and quintet (5dd) states were revealed in the spectrum of 3. The results are interpreted in terms of a peculiar nature of transition metal complexes with the unfilled d-shell, where close lying electronic states of different multiplicities may be mixed through configurational, spin−orbit, and vibronic coupling. From the EPR spectra, the spin−orbit coupling constant was estimated to be about 25 cm−1. It is shown that different axial ligation of complexes shifts the relative energy of the excited states and, consequently, leads to population of different states. Plausible explanations of the effects governing unusual spectral and dynamic parameters of the photoexcited Rh corrole complexes are presented.</description><identifier>ISSN: 1089-5639</identifier><identifier>EISSN: 1520-5215</identifier><identifier>DOI: 10.1021/jp909967b</identifier><identifier>PMID: 20070101</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>A: Dynamics, Clusters, Excited States ; Electron Spin Resonance Spectroscopy ; Kinetics ; Ligands ; Molecular Structure ; Organometallic Compounds - chemistry ; Porphyrins - chemistry ; Quantum Theory ; Rhodium - chemistry ; Time Factors</subject><ispartof>The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, 2010-02, Vol.114 (5), p.2059-2072</ispartof><rights>Copyright © 2010 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a310t-51ba6747d596edda1678d7b535275663465a4c9337fb5c38294bd95a5e5bc2d33</citedby><cites>FETCH-LOGICAL-a310t-51ba6747d596edda1678d7b535275663465a4c9337fb5c38294bd95a5e5bc2d33</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/jp909967b$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/jp909967b$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,780,784,2765,27076,27924,27925,56738,56788</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/20070101$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Wagnert, Linn</creatorcontrib><creatorcontrib>Berg, Alexander</creatorcontrib><creatorcontrib>Saltsman, Irena</creatorcontrib><creatorcontrib>Gross, Zeev</creatorcontrib><creatorcontrib>Rozenshtein, Vladimir</creatorcontrib><title>Time-Resolved Electron Paramagnetic Resonance Study of Rhodium(III) Corrole Excited States</title><title>The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory</title><addtitle>J. Phys. Chem. A</addtitle><description>Photoexcited states of three Rh(III) 5,10,15-tris(pentafluorophenyl)corroles coordinated by different axial ligands; namely, triphenylphosphine P(C6H5)3 group (1), pyridine C6H5N group (2), and two pyridine groups (3) were studied by X- and Q-band time-resolved electron paramagnetic resonance (TREPR) in frozen toluene and liquid crystal E-7. Transient mutations were utilized to identify multiplicity of the detected paramagnetic species. The spectra of 1 and 2 were assigned to triplet (3ππ*) states, while contributions of triplet (3dd and charge transfer 3CT) and quintet (5dd) states were revealed in the spectrum of 3. The results are interpreted in terms of a peculiar nature of transition metal complexes with the unfilled d-shell, where close lying electronic states of different multiplicities may be mixed through configurational, spin−orbit, and vibronic coupling. From the EPR spectra, the spin−orbit coupling constant was estimated to be about 25 cm−1. It is shown that different axial ligation of complexes shifts the relative energy of the excited states and, consequently, leads to population of different states. Plausible explanations of the effects governing unusual spectral and dynamic parameters of the photoexcited Rh corrole complexes are presented.</description><subject>A: Dynamics, Clusters, Excited States</subject><subject>Electron Spin Resonance Spectroscopy</subject><subject>Kinetics</subject><subject>Ligands</subject><subject>Molecular Structure</subject><subject>Organometallic Compounds - chemistry</subject><subject>Porphyrins - chemistry</subject><subject>Quantum Theory</subject><subject>Rhodium - chemistry</subject><subject>Time Factors</subject><issn>1089-5639</issn><issn>1520-5215</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2010</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNptkM9LwzAUgIMobk4P_gOSi-gO1fxokuUoY-pgoGzz4qWkSaodbTOTVNx_b8fmTp7eg_fxwfsAuMToDiOC71driaTkIj8CfcwIShjB7Ljb0UgmjFPZA2chrBBCmJL0FPQIQgJhhPvgfVnWNpnb4Kpva-Cksjp618BX5VWtPhobSw2350Y12sJFbM0GugLOP50p2_p2Op0O4dh57yoLJz-6jJ1lEVW04RycFKoK9mI_B-DtcbIcPyezl6fp-GGWKIpRTBjOFRepMExya4zCXIyMyBllRDDOacqZSrWkVBQ503REZJobyRSzLNfEUDoANzvv2ruv1oaY1WXQtqpUY10bMkE7lSQcd-RwR2rvQvC2yNa-rJXfZBhl25LZoWTHXu2tbV5bcyD_0nXA9Q5QOmQr1_qme_If0S9uaXkN</recordid><startdate>20100211</startdate><enddate>20100211</enddate><creator>Wagnert, Linn</creator><creator>Berg, Alexander</creator><creator>Saltsman, Irena</creator><creator>Gross, Zeev</creator><creator>Rozenshtein, Vladimir</creator><general>American Chemical Society</general><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope></search><sort><creationdate>20100211</creationdate><title>Time-Resolved Electron Paramagnetic Resonance Study of Rhodium(III) Corrole Excited States</title><author>Wagnert, Linn ; Berg, Alexander ; Saltsman, Irena ; Gross, Zeev ; Rozenshtein, Vladimir</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a310t-51ba6747d596edda1678d7b535275663465a4c9337fb5c38294bd95a5e5bc2d33</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2010</creationdate><topic>A: Dynamics, Clusters, Excited States</topic><topic>Electron Spin Resonance Spectroscopy</topic><topic>Kinetics</topic><topic>Ligands</topic><topic>Molecular Structure</topic><topic>Organometallic Compounds - chemistry</topic><topic>Porphyrins - chemistry</topic><topic>Quantum Theory</topic><topic>Rhodium - chemistry</topic><topic>Time Factors</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Wagnert, Linn</creatorcontrib><creatorcontrib>Berg, Alexander</creatorcontrib><creatorcontrib>Saltsman, Irena</creatorcontrib><creatorcontrib>Gross, Zeev</creatorcontrib><creatorcontrib>Rozenshtein, Vladimir</creatorcontrib><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Wagnert, Linn</au><au>Berg, Alexander</au><au>Saltsman, Irena</au><au>Gross, Zeev</au><au>Rozenshtein, Vladimir</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Time-Resolved Electron Paramagnetic Resonance Study of Rhodium(III) Corrole Excited States</atitle><jtitle>The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory</jtitle><addtitle>J. Phys. Chem. A</addtitle><date>2010-02-11</date><risdate>2010</risdate><volume>114</volume><issue>5</issue><spage>2059</spage><epage>2072</epage><pages>2059-2072</pages><issn>1089-5639</issn><eissn>1520-5215</eissn><abstract>Photoexcited states of three Rh(III) 5,10,15-tris(pentafluorophenyl)corroles coordinated by different axial ligands; namely, triphenylphosphine P(C6H5)3 group (1), pyridine C6H5N group (2), and two pyridine groups (3) were studied by X- and Q-band time-resolved electron paramagnetic resonance (TREPR) in frozen toluene and liquid crystal E-7. Transient mutations were utilized to identify multiplicity of the detected paramagnetic species. The spectra of 1 and 2 were assigned to triplet (3ππ*) states, while contributions of triplet (3dd and charge transfer 3CT) and quintet (5dd) states were revealed in the spectrum of 3. The results are interpreted in terms of a peculiar nature of transition metal complexes with the unfilled d-shell, where close lying electronic states of different multiplicities may be mixed through configurational, spin−orbit, and vibronic coupling. From the EPR spectra, the spin−orbit coupling constant was estimated to be about 25 cm−1. It is shown that different axial ligation of complexes shifts the relative energy of the excited states and, consequently, leads to population of different states. Plausible explanations of the effects governing unusual spectral and dynamic parameters of the photoexcited Rh corrole complexes are presented.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>20070101</pmid><doi>10.1021/jp909967b</doi><tpages>14</tpages></addata></record> |
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subjects | A: Dynamics, Clusters, Excited States Electron Spin Resonance Spectroscopy Kinetics Ligands Molecular Structure Organometallic Compounds - chemistry Porphyrins - chemistry Quantum Theory Rhodium - chemistry Time Factors |
title | Time-Resolved Electron Paramagnetic Resonance Study of Rhodium(III) Corrole Excited States |
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