Photoinduced organic donor to metal electron transfer across a rigid spacer
Two compounds (b)ReCH-DTF, which contain the metal complex chromophore (b)Re{sup I}(CO){sub 3} (where b = 2,2{prime}-bipyrazine or 5,5{prime}-bis(N,N-diethylcarbamido)-2,2{prime}-bipyridine) covalently linked to a 1,3-benzodithiafulvene (DTF) electron donor via a trans-1,4-cyclohexane (CH) spacer, h...
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| Veröffentlicht in: | Journal of physical chemistry (1952) 1990-12, Vol.94 (25), p.8745-8748 |
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| container_issue | 25 |
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| container_title | Journal of physical chemistry (1952) |
| container_volume | 94 |
| creator | Perkins, Thomas A Hauser, Brian T Eyler, John R Schanze, Kirk S |
| description | Two compounds (b)ReCH-DTF, which contain the metal complex chromophore (b)Re{sup I}(CO){sub 3} (where b = 2,2{prime}-bipyrazine or 5,5{prime}-bis(N,N-diethylcarbamido)-2,2{prime}-bipyridine) covalently linked to a 1,3-benzodithiafulvene (DTF) electron donor via a trans-1,4-cyclohexane (CH) spacer, have been prepared and studied by emission and transient absorption spectroscopy. Steady-state and time-resolved emission data indicate that the metal-to-ligand charge-transfer (MLCT) excited state of the (b)ReCH-DTF complexes is quenched compared to the model compounds (b)ReCH which contain the (b)Re{sup I}(CO){sub 3} chromophore but not the DTF donor. The MLCT quenching is ascribed to a rapid intramolecular DTF {yields} Re electron transfer (ET) which competes with normal radiative and nonradiative MLCT decay. The occurrence of intramolecular ET is confirmed by nanosecond transient absorption studies which reveal that the charge-transfer state, (b{sup {sm bullet}{minus}})Re{sup I}(CO){sub 3}-CH-DTF{sup {sm bullet}+}, is formed rapidly following photoexcitation. |
| doi_str_mv | 10.1021/j100388a001 |
| format | Article |
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Steady-state and time-resolved emission data indicate that the metal-to-ligand charge-transfer (MLCT) excited state of the (b)ReCH-DTF complexes is quenched compared to the model compounds (b)ReCH which contain the (b)Re{sup I}(CO){sub 3} chromophore but not the DTF donor. The MLCT quenching is ascribed to a rapid intramolecular DTF {yields} Re electron transfer (ET) which competes with normal radiative and nonradiative MLCT decay. The occurrence of intramolecular ET is confirmed by nanosecond transient absorption studies which reveal that the charge-transfer state, (b{sup {sm bullet}{minus}})Re{sup I}(CO){sub 3}-CH-DTF{sup {sm bullet}+}, is formed rapidly following photoexcitation.</description><identifier>ISSN: 0022-3654</identifier><identifier>EISSN: 1541-5740</identifier><identifier>DOI: 10.1021/j100388a001</identifier><identifier>CODEN: JPCHAX</identifier><language>eng</language><publisher>Washington, DC: American Chemical Society</publisher><subject>400201 - Chemical & Physicochemical Properties ; 400500 - Photochemistry ; ABSORPTION SPECTROSCOPY ; AZINES ; BIPYRIDINES ; CHEMICAL REACTIONS ; Chemistry ; DATA ; ELECTRON TRANSFER ; ENERGY LEVELS ; Exact sciences and technology ; EXCITED STATES ; EXPERIMENTAL DATA ; General and physical chemistry ; HETEROCYCLIC COMPOUNDS ; INFORMATION ; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ; MEASURING METHODS ; NUMERICAL DATA ; ORGANIC COMPOUNDS ; ORGANIC NITROGEN COMPOUNDS ; PHOTOCHEMICAL REACTIONS ; Physical chemistry of induced reactions (with radiations, particles and ultrasonics) ; PYRIDINES ; SPECTROSCOPY</subject><ispartof>Journal of physical chemistry (1952), 1990-12, Vol.94 (25), p.8745-8748</ispartof><rights>1993 INIST-CNRS</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a357t-2e185ef57009f02243559a37f442af102b792d49ffd007bb0dc33bdc3821d0b93</citedby></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/j100388a001$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/j100388a001$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>230,314,780,784,885,2765,27076,27924,27925,56738,56788</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=4402761$$DView record in Pascal Francis$$Hfree_for_read</backlink><backlink>$$Uhttps://www.osti.gov/biblio/6108122$$D View this record in Osti.gov$$Hfree_for_read</backlink></links><search><creatorcontrib>Perkins, Thomas A</creatorcontrib><creatorcontrib>Hauser, Brian T</creatorcontrib><creatorcontrib>Eyler, John R</creatorcontrib><creatorcontrib>Schanze, Kirk S</creatorcontrib><title>Photoinduced organic donor to metal electron transfer across a rigid spacer</title><title>Journal of physical chemistry (1952)</title><addtitle>J. Phys. Chem</addtitle><description>Two compounds (b)ReCH-DTF, which contain the metal complex chromophore (b)Re{sup I}(CO){sub 3} (where b = 2,2{prime}-bipyrazine or 5,5{prime}-bis(N,N-diethylcarbamido)-2,2{prime}-bipyridine) covalently linked to a 1,3-benzodithiafulvene (DTF) electron donor via a trans-1,4-cyclohexane (CH) spacer, have been prepared and studied by emission and transient absorption spectroscopy. Steady-state and time-resolved emission data indicate that the metal-to-ligand charge-transfer (MLCT) excited state of the (b)ReCH-DTF complexes is quenched compared to the model compounds (b)ReCH which contain the (b)Re{sup I}(CO){sub 3} chromophore but not the DTF donor. The MLCT quenching is ascribed to a rapid intramolecular DTF {yields} Re electron transfer (ET) which competes with normal radiative and nonradiative MLCT decay. The occurrence of intramolecular ET is confirmed by nanosecond transient absorption studies which reveal that the charge-transfer state, (b{sup {sm bullet}{minus}})Re{sup I}(CO){sub 3}-CH-DTF{sup {sm bullet}+}, is formed rapidly following photoexcitation.</description><subject>400201 - Chemical & Physicochemical Properties</subject><subject>400500 - Photochemistry</subject><subject>ABSORPTION SPECTROSCOPY</subject><subject>AZINES</subject><subject>BIPYRIDINES</subject><subject>CHEMICAL REACTIONS</subject><subject>Chemistry</subject><subject>DATA</subject><subject>ELECTRON TRANSFER</subject><subject>ENERGY LEVELS</subject><subject>Exact sciences and technology</subject><subject>EXCITED STATES</subject><subject>EXPERIMENTAL DATA</subject><subject>General and physical chemistry</subject><subject>HETEROCYCLIC COMPOUNDS</subject><subject>INFORMATION</subject><subject>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</subject><subject>MEASURING METHODS</subject><subject>NUMERICAL DATA</subject><subject>ORGANIC COMPOUNDS</subject><subject>ORGANIC NITROGEN COMPOUNDS</subject><subject>PHOTOCHEMICAL REACTIONS</subject><subject>Physical chemistry of induced reactions (with radiations, particles and ultrasonics)</subject><subject>PYRIDINES</subject><subject>SPECTROSCOPY</subject><issn>0022-3654</issn><issn>1541-5740</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1990</creationdate><recordtype>article</recordtype><recordid>eNpt0MtKAzEUBuAgCtbLyhcIIriQ0ZNbM7NUUSsKFqx0GTKZpKbWSUki6NsbHREXbpJFvhP-8yN0QOCUACVnSwLA6loDkA00IoKTSkgOm2gEQGnFxoJvo52UllAEY2SE7qbPIQffd2_GdjjEhe69wV3oQ8Q54Feb9QrblTU5hh7nqPvkbMTaxJAS1jj6he9wWmtj4x7acnqV7P7PvYuerq9ml5Pq_uHm9vL8vtJMyFxRS2phnZAAjSuxOBOi0Uw6zql2ZY9WNrTjjXMdgGxb6AxjbTlqSjpoG7aLDod_Q8peJeOzNc8m9H1JqcYEakJpQScD-k4arVPr6F91_FAE1FdZ6k9ZRR8Neq2T0StX9jQ-_Y5wDlSOv1g1MJ-yff991vFFjSWTQs2mj2p-MRWTRzpXdfHHg9cmqWV4i33p5d8An2WMgyc</recordid><startdate>19901201</startdate><enddate>19901201</enddate><creator>Perkins, Thomas A</creator><creator>Hauser, Brian T</creator><creator>Eyler, John R</creator><creator>Schanze, Kirk S</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>IQODW</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>OTOTI</scope></search><sort><creationdate>19901201</creationdate><title>Photoinduced organic donor to metal electron transfer across a rigid spacer</title><author>Perkins, Thomas A ; Hauser, Brian T ; Eyler, John R ; Schanze, Kirk S</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a357t-2e185ef57009f02243559a37f442af102b792d49ffd007bb0dc33bdc3821d0b93</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>1990</creationdate><topic>400201 - Chemical & Physicochemical Properties</topic><topic>400500 - Photochemistry</topic><topic>ABSORPTION SPECTROSCOPY</topic><topic>AZINES</topic><topic>BIPYRIDINES</topic><topic>CHEMICAL REACTIONS</topic><topic>Chemistry</topic><topic>DATA</topic><topic>ELECTRON TRANSFER</topic><topic>ENERGY LEVELS</topic><topic>Exact sciences and technology</topic><topic>EXCITED STATES</topic><topic>EXPERIMENTAL DATA</topic><topic>General and physical chemistry</topic><topic>HETEROCYCLIC COMPOUNDS</topic><topic>INFORMATION</topic><topic>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</topic><topic>MEASURING METHODS</topic><topic>NUMERICAL DATA</topic><topic>ORGANIC COMPOUNDS</topic><topic>ORGANIC NITROGEN COMPOUNDS</topic><topic>PHOTOCHEMICAL REACTIONS</topic><topic>Physical chemistry of induced reactions (with radiations, particles and ultrasonics)</topic><topic>PYRIDINES</topic><topic>SPECTROSCOPY</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Perkins, Thomas A</creatorcontrib><creatorcontrib>Hauser, Brian T</creatorcontrib><creatorcontrib>Eyler, John R</creatorcontrib><creatorcontrib>Schanze, Kirk S</creatorcontrib><collection>Istex</collection><collection>Pascal-Francis</collection><collection>CrossRef</collection><collection>OSTI.GOV</collection><jtitle>Journal of physical chemistry (1952)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Perkins, Thomas A</au><au>Hauser, Brian T</au><au>Eyler, John R</au><au>Schanze, Kirk S</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Photoinduced organic donor to metal electron transfer across a rigid spacer</atitle><jtitle>Journal of physical chemistry (1952)</jtitle><addtitle>J. Phys. Chem</addtitle><date>1990-12-01</date><risdate>1990</risdate><volume>94</volume><issue>25</issue><spage>8745</spage><epage>8748</epage><pages>8745-8748</pages><issn>0022-3654</issn><eissn>1541-5740</eissn><coden>JPCHAX</coden><abstract>Two compounds (b)ReCH-DTF, which contain the metal complex chromophore (b)Re{sup I}(CO){sub 3} (where b = 2,2{prime}-bipyrazine or 5,5{prime}-bis(N,N-diethylcarbamido)-2,2{prime}-bipyridine) covalently linked to a 1,3-benzodithiafulvene (DTF) electron donor via a trans-1,4-cyclohexane (CH) spacer, have been prepared and studied by emission and transient absorption spectroscopy. Steady-state and time-resolved emission data indicate that the metal-to-ligand charge-transfer (MLCT) excited state of the (b)ReCH-DTF complexes is quenched compared to the model compounds (b)ReCH which contain the (b)Re{sup I}(CO){sub 3} chromophore but not the DTF donor. The MLCT quenching is ascribed to a rapid intramolecular DTF {yields} Re electron transfer (ET) which competes with normal radiative and nonradiative MLCT decay. The occurrence of intramolecular ET is confirmed by nanosecond transient absorption studies which reveal that the charge-transfer state, (b{sup {sm bullet}{minus}})Re{sup I}(CO){sub 3}-CH-DTF{sup {sm bullet}+}, is formed rapidly following photoexcitation.</abstract><cop>Washington, DC</cop><pub>American Chemical Society</pub><doi>10.1021/j100388a001</doi><tpages>4</tpages></addata></record> |
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| source | ACS Publications |
| subjects | 400201 - Chemical & Physicochemical Properties 400500 - Photochemistry ABSORPTION SPECTROSCOPY AZINES BIPYRIDINES CHEMICAL REACTIONS Chemistry DATA ELECTRON TRANSFER ENERGY LEVELS Exact sciences and technology EXCITED STATES EXPERIMENTAL DATA General and physical chemistry HETEROCYCLIC COMPOUNDS INFORMATION INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY MEASURING METHODS NUMERICAL DATA ORGANIC COMPOUNDS ORGANIC NITROGEN COMPOUNDS PHOTOCHEMICAL REACTIONS Physical chemistry of induced reactions (with radiations, particles and ultrasonics) PYRIDINES SPECTROSCOPY |
| title | Photoinduced organic donor to metal electron transfer across a rigid spacer |
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