Solvent dependence of excited-state proton transfer from pyranine-derived photoacids
Steady-state and time-resolved techniques were employed to study the excited-state proton-transfer (ESPT) rate of two newly synthesized 8-hydroxy-1,3,6-pyrenetrisulfonate (pyranine, HPTS) derived photoacids in three protic solvents, water, methanol and ethanol. The ESPT rate constant k(PT) of tris(1...
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| Veröffentlicht in: | Physical chemistry chemical physics : PCCP 2014-05, Vol.16 (19), p.9104-9114 |
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| creator | Spies, Christian Shomer, Shay Finkler, Björn Pines, Dina Pines, Ehud Jung, Gregor Huppert, Dan |
| description | Steady-state and time-resolved techniques were employed to study the excited-state proton-transfer (ESPT) rate of two newly synthesized 8-hydroxy-1,3,6-pyrenetrisulfonate (pyranine, HPTS) derived photoacids in three protic solvents, water, methanol and ethanol. The ESPT rate constant k(PT) of tris(1,1,1,3,3,3-hexafluoropropan-2-yl)-8-hydroxypyrene-1,3,6-trisulfonate, 1a, whose pK(a)* ~ -4, in water, methanol and ethanol is 3 × 10(11) s(-1), 8 × 10(9) s(-1) and 5 × 10(9) s(-1) respectively. (8-Hydroxy-N1,N3,N6-tris(2-hydroxyethyl)-N1,N3,N6-trimethylpyrene-1,3,6 trisulfonamide, 1b) is a weaker acid than 1a but still a strong photoacid with pK(a)* ~ -1 and the ESPT rate in water, methanol and ethanol is 7 × 10(10) s(-1), 4 × 10(8) s(-1) and 2 × 10(8) s(-1). We qualitatively explain our kinetic results by a Marcus-like free-energy correlation which was found to have a general form suitable for describing proton transfer reactions in both the proton-adiabatic and the proton-non-adiabatic limits. |
| doi_str_mv | 10.1039/c3cp55292f |
| format | Article |
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The ESPT rate constant k(PT) of tris(1,1,1,3,3,3-hexafluoropropan-2-yl)-8-hydroxypyrene-1,3,6-trisulfonate, 1a, whose pK(a)* ~ -4, in water, methanol and ethanol is 3 × 10(11) s(-1), 8 × 10(9) s(-1) and 5 × 10(9) s(-1) respectively. (8-Hydroxy-N1,N3,N6-tris(2-hydroxyethyl)-N1,N3,N6-trimethylpyrene-1,3,6 trisulfonamide, 1b) is a weaker acid than 1a but still a strong photoacid with pK(a)* ~ -1 and the ESPT rate in water, methanol and ethanol is 7 × 10(10) s(-1), 4 × 10(8) s(-1) and 2 × 10(8) s(-1). We qualitatively explain our kinetic results by a Marcus-like free-energy correlation which was found to have a general form suitable for describing proton transfer reactions in both the proton-adiabatic and the proton-non-adiabatic limits.</description><identifier>ISSN: 1463-9076</identifier><identifier>EISSN: 1463-9084</identifier><identifier>DOI: 10.1039/c3cp55292f</identifier><identifier>PMID: 24700348</identifier><language>eng</language><publisher>England</publisher><subject>Acids - chemistry ; Arylsulfonates - chemical synthesis ; Arylsulfonates - chemistry ; Correlation ; Ethanol ; Ethanol - chemistry ; Ethyl alcohol ; Excitation ; Kinetics ; Methanol - chemistry ; Methyl alcohol ; Photochemical Processes ; Physical chemistry ; Protons ; Rate constants ; Solvents ; Solvents - chemistry ; Water - chemistry</subject><ispartof>Physical chemistry chemical physics : PCCP, 2014-05, Vol.16 (19), p.9104-9114</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c357t-1f000ef1a275494934c499ab043dfddc62c840b6c8ff43dd25549c39a6ec1b763</citedby><cites>FETCH-LOGICAL-c357t-1f000ef1a275494934c499ab043dfddc62c840b6c8ff43dd25549c39a6ec1b763</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,27924,27925</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/24700348$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Spies, Christian</creatorcontrib><creatorcontrib>Shomer, Shay</creatorcontrib><creatorcontrib>Finkler, Björn</creatorcontrib><creatorcontrib>Pines, Dina</creatorcontrib><creatorcontrib>Pines, Ehud</creatorcontrib><creatorcontrib>Jung, Gregor</creatorcontrib><creatorcontrib>Huppert, Dan</creatorcontrib><title>Solvent dependence of excited-state proton transfer from pyranine-derived photoacids</title><title>Physical chemistry chemical physics : PCCP</title><addtitle>Phys Chem Chem Phys</addtitle><description>Steady-state and time-resolved techniques were employed to study the excited-state proton-transfer (ESPT) rate of two newly synthesized 8-hydroxy-1,3,6-pyrenetrisulfonate (pyranine, HPTS) derived photoacids in three protic solvents, water, methanol and ethanol. The ESPT rate constant k(PT) of tris(1,1,1,3,3,3-hexafluoropropan-2-yl)-8-hydroxypyrene-1,3,6-trisulfonate, 1a, whose pK(a)* ~ -4, in water, methanol and ethanol is 3 × 10(11) s(-1), 8 × 10(9) s(-1) and 5 × 10(9) s(-1) respectively. (8-Hydroxy-N1,N3,N6-tris(2-hydroxyethyl)-N1,N3,N6-trimethylpyrene-1,3,6 trisulfonamide, 1b) is a weaker acid than 1a but still a strong photoacid with pK(a)* ~ -1 and the ESPT rate in water, methanol and ethanol is 7 × 10(10) s(-1), 4 × 10(8) s(-1) and 2 × 10(8) s(-1). We qualitatively explain our kinetic results by a Marcus-like free-energy correlation which was found to have a general form suitable for describing proton transfer reactions in both the proton-adiabatic and the proton-non-adiabatic limits.</description><subject>Acids - chemistry</subject><subject>Arylsulfonates - chemical synthesis</subject><subject>Arylsulfonates - chemistry</subject><subject>Correlation</subject><subject>Ethanol</subject><subject>Ethanol - chemistry</subject><subject>Ethyl alcohol</subject><subject>Excitation</subject><subject>Kinetics</subject><subject>Methanol - chemistry</subject><subject>Methyl alcohol</subject><subject>Photochemical Processes</subject><subject>Physical chemistry</subject><subject>Protons</subject><subject>Rate constants</subject><subject>Solvents</subject><subject>Solvents - chemistry</subject><subject>Water - chemistry</subject><issn>1463-9076</issn><issn>1463-9084</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2014</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNqFkEtLAzEUhYMotlY3_gDJUoTRZJJ5ZCnFFxRcWNdDJrnBkZlkTNJi_73R1rp0dR98HM45CJ1Tck0JEzeKqbEocpGbAzSlvGSZIDU_3O9VOUEnIbwTQmhB2TGa5LwihPF6ipYvrl-DjVjDCFaDVYCdwfCpugg6C1FGwKN30VkcvbTBgMfGuwGPm3R2FjINvluDxuNboqTqdDhFR0b2Ac52c4Ze7--W88ds8fzwNL9dZIoVVcyoSY7AUJlXBRdcMK64ELIlnGmjtSpzVXPSlqo2Jr10XiRMMSFLULStSjZDl1vdZPBjBSE2QxcU9L204FahoQWnPGdlCv0_SismavqDXm1R5V0IHkwz-m6QftNQ0nwX3vwVnuCLne6qHUDv0d-G2RftpXwp</recordid><startdate>20140521</startdate><enddate>20140521</enddate><creator>Spies, Christian</creator><creator>Shomer, Shay</creator><creator>Finkler, Björn</creator><creator>Pines, Dina</creator><creator>Pines, Ehud</creator><creator>Jung, Gregor</creator><creator>Huppert, Dan</creator><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><scope>7U5</scope><scope>8FD</scope><scope>L7M</scope></search><sort><creationdate>20140521</creationdate><title>Solvent dependence of excited-state proton transfer from pyranine-derived photoacids</title><author>Spies, Christian ; Shomer, Shay ; Finkler, Björn ; Pines, Dina ; Pines, Ehud ; Jung, Gregor ; Huppert, Dan</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c357t-1f000ef1a275494934c499ab043dfddc62c840b6c8ff43dd25549c39a6ec1b763</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2014</creationdate><topic>Acids - chemistry</topic><topic>Arylsulfonates - chemical synthesis</topic><topic>Arylsulfonates - chemistry</topic><topic>Correlation</topic><topic>Ethanol</topic><topic>Ethanol - chemistry</topic><topic>Ethyl alcohol</topic><topic>Excitation</topic><topic>Kinetics</topic><topic>Methanol - chemistry</topic><topic>Methyl alcohol</topic><topic>Photochemical Processes</topic><topic>Physical chemistry</topic><topic>Protons</topic><topic>Rate constants</topic><topic>Solvents</topic><topic>Solvents - chemistry</topic><topic>Water - chemistry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Spies, Christian</creatorcontrib><creatorcontrib>Shomer, Shay</creatorcontrib><creatorcontrib>Finkler, Björn</creatorcontrib><creatorcontrib>Pines, Dina</creatorcontrib><creatorcontrib>Pines, Ehud</creatorcontrib><creatorcontrib>Jung, Gregor</creatorcontrib><creatorcontrib>Huppert, Dan</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><collection>Solid State and Superconductivity Abstracts</collection><collection>Technology Research Database</collection><collection>Advanced Technologies Database with Aerospace</collection><jtitle>Physical chemistry chemical physics : PCCP</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Spies, Christian</au><au>Shomer, Shay</au><au>Finkler, Björn</au><au>Pines, Dina</au><au>Pines, Ehud</au><au>Jung, Gregor</au><au>Huppert, Dan</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Solvent dependence of excited-state proton transfer from pyranine-derived photoacids</atitle><jtitle>Physical chemistry chemical physics : PCCP</jtitle><addtitle>Phys Chem Chem Phys</addtitle><date>2014-05-21</date><risdate>2014</risdate><volume>16</volume><issue>19</issue><spage>9104</spage><epage>9114</epage><pages>9104-9114</pages><issn>1463-9076</issn><eissn>1463-9084</eissn><abstract>Steady-state and time-resolved techniques were employed to study the excited-state proton-transfer (ESPT) rate of two newly synthesized 8-hydroxy-1,3,6-pyrenetrisulfonate (pyranine, HPTS) derived photoacids in three protic solvents, water, methanol and ethanol. The ESPT rate constant k(PT) of tris(1,1,1,3,3,3-hexafluoropropan-2-yl)-8-hydroxypyrene-1,3,6-trisulfonate, 1a, whose pK(a)* ~ -4, in water, methanol and ethanol is 3 × 10(11) s(-1), 8 × 10(9) s(-1) and 5 × 10(9) s(-1) respectively. (8-Hydroxy-N1,N3,N6-tris(2-hydroxyethyl)-N1,N3,N6-trimethylpyrene-1,3,6 trisulfonamide, 1b) is a weaker acid than 1a but still a strong photoacid with pK(a)* ~ -1 and the ESPT rate in water, methanol and ethanol is 7 × 10(10) s(-1), 4 × 10(8) s(-1) and 2 × 10(8) s(-1). We qualitatively explain our kinetic results by a Marcus-like free-energy correlation which was found to have a general form suitable for describing proton transfer reactions in both the proton-adiabatic and the proton-non-adiabatic limits.</abstract><cop>England</cop><pmid>24700348</pmid><doi>10.1039/c3cp55292f</doi><tpages>11</tpages></addata></record> |
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| source | MEDLINE; Royal Society Of Chemistry Journals; Alma/SFX Local Collection |
| subjects | Acids - chemistry Arylsulfonates - chemical synthesis Arylsulfonates - chemistry Correlation Ethanol Ethanol - chemistry Ethyl alcohol Excitation Kinetics Methanol - chemistry Methyl alcohol Photochemical Processes Physical chemistry Protons Rate constants Solvents Solvents - chemistry Water - chemistry |
| title | Solvent dependence of excited-state proton transfer from pyranine-derived photoacids |
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