Photoinduced Electron Transfer in Covalently Linked 1,8-Naphthalimide/Viologen Systems
A series of polymethylene-linked 1,8-naphthalimide/viologen diads has been synthesized. The number of intervening methylenes was varied from 2 to 6. For comparison, a series of N-alkylpyridiniumyl-1,8-naphthalimide “parent” compounds was prepared and photophysically characterized. Relative to the pa...
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Veröffentlicht in: | The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2000-07, Vol.104 (29), p.6778-6785 |
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description | A series of polymethylene-linked 1,8-naphthalimide/viologen diads has been synthesized. The number of intervening methylenes was varied from 2 to 6. For comparison, a series of N-alkylpyridiniumyl-1,8-naphthalimide “parent” compounds was prepared and photophysically characterized. Relative to the parent compounds, the electronically excited singlet state of the 1,8-naphthalimide was found to be quenched by the covalently attached viologen. From Stern−Volmer analyses of the steady-state fluorescence spectra, along with the singlet-state lifetime of the pyridinium-substituted 1,8-naphthalimide, the rate constants for intramolecular quenching were calculated to range from 1.5 × 1010 s-1 (2 intervening methylenes) to 8.3 × 107 s-1 (6 intervening methylenes) in aqueous buffered solution. For comparison, the intermolecular reactivity of the excited singlet state of N-alkylpyridiniumyl-1,8-naphthalimides with methylviologen was assessed. In 0.5 M phosphate buffer (pH 7.0), the bimolecular rate constant was found to be 3.2 × 109 M-1 s-1. Nanosecond laser flash photolysis studies were carried out to identify the quenching products. From these studies, reduced methylviologen was identified as a singlet-state quenching product. From these results, we attribute both the intra- and intermolecular quenching process to electron transfer from the singlet excited state of 1,8-naphthalimide to methylviologen. Within the covalently linked series, the rate constant for intramolecular electron transfer was found to vary exponentially with the number of intervening methylenes. Linear least-squares analysis of the results yielded an apparent β value of 1.04 Å-1 for electron transfer through the polymethylene bridge. |
doi_str_mv | 10.1021/jp000855y |
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The number of intervening methylenes was varied from 2 to 6. For comparison, a series of N-alkylpyridiniumyl-1,8-naphthalimide “parent” compounds was prepared and photophysically characterized. Relative to the parent compounds, the electronically excited singlet state of the 1,8-naphthalimide was found to be quenched by the covalently attached viologen. From Stern−Volmer analyses of the steady-state fluorescence spectra, along with the singlet-state lifetime of the pyridinium-substituted 1,8-naphthalimide, the rate constants for intramolecular quenching were calculated to range from 1.5 × 1010 s-1 (2 intervening methylenes) to 8.3 × 107 s-1 (6 intervening methylenes) in aqueous buffered solution. For comparison, the intermolecular reactivity of the excited singlet state of N-alkylpyridiniumyl-1,8-naphthalimides with methylviologen was assessed. In 0.5 M phosphate buffer (pH 7.0), the bimolecular rate constant was found to be 3.2 × 109 M-1 s-1. Nanosecond laser flash photolysis studies were carried out to identify the quenching products. From these studies, reduced methylviologen was identified as a singlet-state quenching product. From these results, we attribute both the intra- and intermolecular quenching process to electron transfer from the singlet excited state of 1,8-naphthalimide to methylviologen. Within the covalently linked series, the rate constant for intramolecular electron transfer was found to vary exponentially with the number of intervening methylenes. Linear least-squares analysis of the results yielded an apparent β value of 1.04 Å-1 for electron transfer through the polymethylene bridge.</description><identifier>ISSN: 1089-5639</identifier><identifier>EISSN: 1520-5215</identifier><identifier>DOI: 10.1021/jp000855y</identifier><language>eng</language><publisher>American Chemical Society</publisher><ispartof>The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, 2000-07, Vol.104 (29), p.6778-6785</ispartof><rights>Copyright © 2000 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a295t-288cf5431c641552b791258da99436ace21c53248ddb7ea68870640848d02c7f3</citedby><cites>FETCH-LOGICAL-a295t-288cf5431c641552b791258da99436ace21c53248ddb7ea68870640848d02c7f3</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/jp000855y$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/jp000855y$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,780,784,2763,27075,27923,27924,56737,56787</link.rule.ids></links><search><creatorcontrib>Le, Thao P</creatorcontrib><creatorcontrib>Rogers, Joy E</creatorcontrib><creatorcontrib>Kelly, Lisa A</creatorcontrib><title>Photoinduced Electron Transfer in Covalently Linked 1,8-Naphthalimide/Viologen Systems</title><title>The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory</title><addtitle>J. Phys. Chem. A</addtitle><description>A series of polymethylene-linked 1,8-naphthalimide/viologen diads has been synthesized. The number of intervening methylenes was varied from 2 to 6. For comparison, a series of N-alkylpyridiniumyl-1,8-naphthalimide “parent” compounds was prepared and photophysically characterized. Relative to the parent compounds, the electronically excited singlet state of the 1,8-naphthalimide was found to be quenched by the covalently attached viologen. From Stern−Volmer analyses of the steady-state fluorescence spectra, along with the singlet-state lifetime of the pyridinium-substituted 1,8-naphthalimide, the rate constants for intramolecular quenching were calculated to range from 1.5 × 1010 s-1 (2 intervening methylenes) to 8.3 × 107 s-1 (6 intervening methylenes) in aqueous buffered solution. For comparison, the intermolecular reactivity of the excited singlet state of N-alkylpyridiniumyl-1,8-naphthalimides with methylviologen was assessed. In 0.5 M phosphate buffer (pH 7.0), the bimolecular rate constant was found to be 3.2 × 109 M-1 s-1. Nanosecond laser flash photolysis studies were carried out to identify the quenching products. From these studies, reduced methylviologen was identified as a singlet-state quenching product. From these results, we attribute both the intra- and intermolecular quenching process to electron transfer from the singlet excited state of 1,8-naphthalimide to methylviologen. Within the covalently linked series, the rate constant for intramolecular electron transfer was found to vary exponentially with the number of intervening methylenes. Linear least-squares analysis of the results yielded an apparent β value of 1.04 Å-1 for electron transfer through the polymethylene bridge.</description><issn>1089-5639</issn><issn>1520-5215</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2000</creationdate><recordtype>article</recordtype><recordid>eNpt0MFKAzEQBuAgCtbqwTfYiwfB2CS7ySZHKbUKRautPXgJaTZr026TkmzFfXsjFU-eZhg-hpkfgEuMbjEieLDeIYQ4pd0R6GFKEKQE0-PUIy4gZbk4BWcxrhPCOSl6YDFd-dZbV-21qbJRY3QbvMvmQblYm5BZlw39p2qMa5sum1i3SQzfcPikdqt2pRq7tZUZLKxv_Idx2ayLrdnGc3BSqyaai9_aB2_3o_nwAU6ex4_DuwlURNAWEs51TYsca1ZgSsmyFJhQXikhipwpbQjWNN3Jq2pZGsU4LxErEE8DRHRZ531wfdirg48xmFrugt2q0EmM5E8g8i-QZOHB2nTi1x9UYSNZmZdUzqcz-SIIK8T7qxwnf3XwSke59vvg0if_7P0GoCht1A</recordid><startdate>20000727</startdate><enddate>20000727</enddate><creator>Le, Thao P</creator><creator>Rogers, Joy E</creator><creator>Kelly, Lisa A</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>AAYXX</scope><scope>CITATION</scope></search><sort><creationdate>20000727</creationdate><title>Photoinduced Electron Transfer in Covalently Linked 1,8-Naphthalimide/Viologen Systems</title><author>Le, Thao P ; Rogers, Joy E ; Kelly, Lisa A</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a295t-288cf5431c641552b791258da99436ace21c53248ddb7ea68870640848d02c7f3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2000</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Le, Thao P</creatorcontrib><creatorcontrib>Rogers, Joy E</creatorcontrib><creatorcontrib>Kelly, Lisa A</creatorcontrib><collection>Istex</collection><collection>CrossRef</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>Le, Thao P</au><au>Rogers, Joy E</au><au>Kelly, Lisa A</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Photoinduced Electron Transfer in Covalently Linked 1,8-Naphthalimide/Viologen Systems</atitle><jtitle>The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory</jtitle><addtitle>J. Phys. Chem. A</addtitle><date>2000-07-27</date><risdate>2000</risdate><volume>104</volume><issue>29</issue><spage>6778</spage><epage>6785</epage><pages>6778-6785</pages><issn>1089-5639</issn><eissn>1520-5215</eissn><abstract>A series of polymethylene-linked 1,8-naphthalimide/viologen diads has been synthesized. The number of intervening methylenes was varied from 2 to 6. For comparison, a series of N-alkylpyridiniumyl-1,8-naphthalimide “parent” compounds was prepared and photophysically characterized. Relative to the parent compounds, the electronically excited singlet state of the 1,8-naphthalimide was found to be quenched by the covalently attached viologen. From Stern−Volmer analyses of the steady-state fluorescence spectra, along with the singlet-state lifetime of the pyridinium-substituted 1,8-naphthalimide, the rate constants for intramolecular quenching were calculated to range from 1.5 × 1010 s-1 (2 intervening methylenes) to 8.3 × 107 s-1 (6 intervening methylenes) in aqueous buffered solution. For comparison, the intermolecular reactivity of the excited singlet state of N-alkylpyridiniumyl-1,8-naphthalimides with methylviologen was assessed. In 0.5 M phosphate buffer (pH 7.0), the bimolecular rate constant was found to be 3.2 × 109 M-1 s-1. Nanosecond laser flash photolysis studies were carried out to identify the quenching products. From these studies, reduced methylviologen was identified as a singlet-state quenching product. From these results, we attribute both the intra- and intermolecular quenching process to electron transfer from the singlet excited state of 1,8-naphthalimide to methylviologen. Within the covalently linked series, the rate constant for intramolecular electron transfer was found to vary exponentially with the number of intervening methylenes. Linear least-squares analysis of the results yielded an apparent β value of 1.04 Å-1 for electron transfer through the polymethylene bridge.</abstract><pub>American Chemical Society</pub><doi>10.1021/jp000855y</doi><tpages>8</tpages></addata></record> |
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title | Photoinduced Electron Transfer in Covalently Linked 1,8-Naphthalimide/Viologen Systems |
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