Long-lived quinone-naphthalene triplet excited complexes: direct measure of rates of proton transfer within intimate radical ion pairs
The quenching of the triplet state of chloranil (tetrachloro-p-benzoquinone) by derivatives of naphthalene in benzene results in the formation of relatively long-lived (/tau/ = 100-350 ns) radical ion pair intermediates. For the electron donor naphthalenes having aliphatic side chain substitution, i...
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| Veröffentlicht in: | J. Phys. Chem.; (United States) 1988-12, Vol.92 (26), p.7174-7177 |
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| container_end_page | 7177 |
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| container_issue | 26 |
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| container_title | J. Phys. Chem.; (United States) |
| container_volume | 92 |
| creator | Jones, Guilford Mouli, Nandini |
| description | The quenching of the triplet state of chloranil (tetrachloro-p-benzoquinone) by derivatives of naphthalene in benzene results in the formation of relatively long-lived (/tau/ = 100-350 ns) radical ion pair intermediates. For the electron donor naphthalenes having aliphatic side chain substitution, intrapair proton transfer can be directly monitored by laser flash photolysis. Measurement of radical ion pair (triplet excited complex) decay times and the quantum yields of resultant semiquinone (OH*) radicals provide rate constants for decay via intersystem crossing (k/sub isc/) and intra-ion-pair proton transfer (k/sub H/). The data reveal relative kinetic acidities of quinone-complexed radical cations and include activation parameters and isotope effects associated with the proton-transfer step. |
| doi_str_mv | 10.1021/j100337a006 |
| format | Article |
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For the electron donor naphthalenes having aliphatic side chain substitution, intrapair proton transfer can be directly monitored by laser flash photolysis. Measurement of radical ion pair (triplet excited complex) decay times and the quantum yields of resultant semiquinone (OH*) radicals provide rate constants for decay via intersystem crossing (k/sub isc/) and intra-ion-pair proton transfer (k/sub H/). The data reveal relative kinetic acidities of quinone-complexed radical cations and include activation parameters and isotope effects associated with the proton-transfer step.</description><identifier>ISSN: 0022-3654</identifier><identifier>EISSN: 1541-5740</identifier><identifier>DOI: 10.1021/j100337a006</identifier><identifier>CODEN: JPCHAX</identifier><language>eng</language><publisher>Washington, DC: American Chemical Society</publisher><subject>400500 - Photochemistry ; ACTIVATION ENERGY ; AROMATICS ; BENZENE ; CHEMICAL REACTIONS ; Chemistry ; CONDENSED AROMATICS ; DATA ; DECOMPOSITION ; ENERGY ; ENERGY LEVELS ; Exact sciences and technology ; EXCITED STATES ; EXPERIMENTAL DATA ; General and physical chemistry ; HYDROCARBONS ; HYDROGEN TRANSFER ; INFORMATION ; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ; ISOTOPE EFFECTS ; LASERS ; LIFETIME ; NAPHTHALENE ; NEODYMIUM LASERS ; NUMERICAL DATA ; ORGANIC COMPOUNDS ; ORGANIC OXYGEN COMPOUNDS ; PHOTOCHEMICAL REACTIONS ; Photochemistry ; PHOTOLYSIS ; Physical chemistry of induced reactions (with radiations, particles and ultrasonics) ; QUINONES ; RYDBERG STATES ; SOLID STATE LASERS</subject><ispartof>J. 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Phys. Chem.; (United States)</title><addtitle>J. Phys. Chem</addtitle><description>The quenching of the triplet state of chloranil (tetrachloro-p-benzoquinone) by derivatives of naphthalene in benzene results in the formation of relatively long-lived (/tau/ = 100-350 ns) radical ion pair intermediates. For the electron donor naphthalenes having aliphatic side chain substitution, intrapair proton transfer can be directly monitored by laser flash photolysis. Measurement of radical ion pair (triplet excited complex) decay times and the quantum yields of resultant semiquinone (OH*) radicals provide rate constants for decay via intersystem crossing (k/sub isc/) and intra-ion-pair proton transfer (k/sub H/). The data reveal relative kinetic acidities of quinone-complexed radical cations and include activation parameters and isotope effects associated with the proton-transfer step.</description><subject>400500 - Photochemistry</subject><subject>ACTIVATION ENERGY</subject><subject>AROMATICS</subject><subject>BENZENE</subject><subject>CHEMICAL REACTIONS</subject><subject>Chemistry</subject><subject>CONDENSED AROMATICS</subject><subject>DATA</subject><subject>DECOMPOSITION</subject><subject>ENERGY</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>HYDROCARBONS</subject><subject>HYDROGEN TRANSFER</subject><subject>INFORMATION</subject><subject>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</subject><subject>ISOTOPE EFFECTS</subject><subject>LASERS</subject><subject>LIFETIME</subject><subject>NAPHTHALENE</subject><subject>NEODYMIUM LASERS</subject><subject>NUMERICAL DATA</subject><subject>ORGANIC COMPOUNDS</subject><subject>ORGANIC OXYGEN COMPOUNDS</subject><subject>PHOTOCHEMICAL REACTIONS</subject><subject>Photochemistry</subject><subject>PHOTOLYSIS</subject><subject>Physical chemistry of induced reactions (with radiations, particles and ultrasonics)</subject><subject>QUINONES</subject><subject>RYDBERG STATES</subject><subject>SOLID STATE LASERS</subject><issn>0022-3654</issn><issn>1541-5740</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1988</creationdate><recordtype>article</recordtype><recordid>eNpt0N1qFDEUB_AgFlxbr3yBIIIXMpqvSWa8k6KtsGChFb0Lp5kzbtbZZEyyun0Bn7tZRooXXiXh_E44_0PIc87ecCb42y1nTEoDjOlHZMVbxZvWKPaYrBgTopG6VU_I05y3jDEuJV-RP-sYvjeT_4UD_bn3IQZsAsybsoEJA9KS_DxhoXhwvlTj4q6-D5jf0cEndIXuEPI-IY0jTVAwHy9ziiWG2gwhj5job182PlAfit9VU-HgHUzUVzSDT_mMnIwwZXz29zwlXz5-uDm_bNafLz6dv183oIQsjRy00oMclXAKBIBoOQgEbA0gsg470_FOmloT_FYbJrqeKe6E0rf9iL2Sp-TF8m_Mxdt8zOQ2LoZQk1jNO93qrqLXC3Ip5pxwtHOqc6c7y5k97tn-s-eqXy56hlwzjTWz8_mhxQjWM91W1izM54KHhzKkH1YbaVp7c3VtO3PRX_L2m_1a_avFg8t2G_cp1L38d4B7P-2Zng</recordid><startdate>198812</startdate><enddate>198812</enddate><creator>Jones, Guilford</creator><creator>Mouli, Nandini</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>IQODW</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>OTOTI</scope></search><sort><creationdate>198812</creationdate><title>Long-lived quinone-naphthalene triplet excited complexes: direct measure of rates of proton transfer within intimate radical ion pairs</title><author>Jones, Guilford ; Mouli, Nandini</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a423t-3d646d3f42c4a2aa251a2eae57aee08e87818374a221b670289041c246b9fe943</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>1988</creationdate><topic>400500 - Photochemistry</topic><topic>ACTIVATION ENERGY</topic><topic>AROMATICS</topic><topic>BENZENE</topic><topic>CHEMICAL REACTIONS</topic><topic>Chemistry</topic><topic>CONDENSED AROMATICS</topic><topic>DATA</topic><topic>DECOMPOSITION</topic><topic>ENERGY</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>HYDROCARBONS</topic><topic>HYDROGEN TRANSFER</topic><topic>INFORMATION</topic><topic>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</topic><topic>ISOTOPE EFFECTS</topic><topic>LASERS</topic><topic>LIFETIME</topic><topic>NAPHTHALENE</topic><topic>NEODYMIUM LASERS</topic><topic>NUMERICAL DATA</topic><topic>ORGANIC COMPOUNDS</topic><topic>ORGANIC OXYGEN COMPOUNDS</topic><topic>PHOTOCHEMICAL REACTIONS</topic><topic>Photochemistry</topic><topic>PHOTOLYSIS</topic><topic>Physical chemistry of induced reactions (with radiations, particles and ultrasonics)</topic><topic>QUINONES</topic><topic>RYDBERG STATES</topic><topic>SOLID STATE LASERS</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Jones, Guilford</creatorcontrib><creatorcontrib>Mouli, Nandini</creatorcontrib><creatorcontrib>Boston Univ., MA (USA)</creatorcontrib><collection>Istex</collection><collection>Pascal-Francis</collection><collection>CrossRef</collection><collection>OSTI.GOV</collection><jtitle>J. Phys. Chem.; (United States)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Jones, Guilford</au><au>Mouli, Nandini</au><aucorp>Boston Univ., MA (USA)</aucorp><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Long-lived quinone-naphthalene triplet excited complexes: direct measure of rates of proton transfer within intimate radical ion pairs</atitle><jtitle>J. Phys. Chem.; (United States)</jtitle><addtitle>J. Phys. Chem</addtitle><date>1988-12</date><risdate>1988</risdate><volume>92</volume><issue>26</issue><spage>7174</spage><epage>7177</epage><pages>7174-7177</pages><issn>0022-3654</issn><eissn>1541-5740</eissn><coden>JPCHAX</coden><abstract>The quenching of the triplet state of chloranil (tetrachloro-p-benzoquinone) by derivatives of naphthalene in benzene results in the formation of relatively long-lived (/tau/ = 100-350 ns) radical ion pair intermediates. For the electron donor naphthalenes having aliphatic side chain substitution, intrapair proton transfer can be directly monitored by laser flash photolysis. Measurement of radical ion pair (triplet excited complex) decay times and the quantum yields of resultant semiquinone (OH*) radicals provide rate constants for decay via intersystem crossing (k/sub isc/) and intra-ion-pair proton transfer (k/sub H/). The data reveal relative kinetic acidities of quinone-complexed radical cations and include activation parameters and isotope effects associated with the proton-transfer step.</abstract><cop>Washington, DC</cop><pub>American Chemical Society</pub><doi>10.1021/j100337a006</doi><tpages>4</tpages></addata></record> |
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| identifier | ISSN: 0022-3654 |
| ispartof | J. Phys. Chem.; (United States), 1988-12, Vol.92 (26), p.7174-7177 |
| issn | 0022-3654 1541-5740 |
| language | eng |
| recordid | cdi_crossref_primary_10_1021_j100337a006 |
| source | American Chemical Society Web Editions |
| subjects | 400500 - Photochemistry ACTIVATION ENERGY AROMATICS BENZENE CHEMICAL REACTIONS Chemistry CONDENSED AROMATICS DATA DECOMPOSITION ENERGY ENERGY LEVELS Exact sciences and technology EXCITED STATES EXPERIMENTAL DATA General and physical chemistry HYDROCARBONS HYDROGEN TRANSFER INFORMATION INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ISOTOPE EFFECTS LASERS LIFETIME NAPHTHALENE NEODYMIUM LASERS NUMERICAL DATA ORGANIC COMPOUNDS ORGANIC OXYGEN COMPOUNDS PHOTOCHEMICAL REACTIONS Photochemistry PHOTOLYSIS Physical chemistry of induced reactions (with radiations, particles and ultrasonics) QUINONES RYDBERG STATES SOLID STATE LASERS |
| title | Long-lived quinone-naphthalene triplet excited complexes: direct measure of rates of proton transfer within intimate radical ion pairs |
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