Time-Resolved Spectroscopy of Sulfur- and Carboxy-Substituted N-Alkylphthalimides
The photophysical and photochemical properties of N‐phthaloylmethionine (1), S‐methyl‐N‐phthaloylcysteine methyl ester (2) and N‐phthaloyltranexamic acid (3) were studied by time‐resolved UV/Vis spectroscopy, using laser pulses at 248 or 308 nm. The quantum yield of fluorescence is low (Φf...
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| Veröffentlicht in: | Chemistry : a European journal 2001-04, Vol.7 (7), p.1530-1538 |
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| container_title | Chemistry : a European journal |
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| creator | Görner, Helmut Griesbeck, Axel G. Heinrich, Thomas Kramer, Wolfgang Oelgemöller, Michael |
| description | The photophysical and photochemical properties of N‐phthaloylmethionine (1), S‐methyl‐N‐phthaloylcysteine methyl ester (2) and N‐phthaloyltranexamic acid (3) were studied by time‐resolved UV/Vis spectroscopy, using laser pulses at 248 or 308 nm. The quantum yield of fluorescence is low (Φf |
| doi_str_mv | 10.1002/1521-3765(20010401)7:7<1530::AID-CHEM1530>3.0.CO;2-L |
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The photophysical and photochemical properties of N‐phthaloylmethionine (1), S‐methyl‐N‐phthaloylcysteine methyl ester (2) and N‐phthaloyltranexamic acid (3) were studied by time‐resolved UV/Vis spectroscopy. The classical Kasha rule (in its photochemical version) seems to be circumvented when observing the chemical behaviour of excited 3.</description><identifier>ISSN: 0947-6539</identifier><identifier>EISSN: 1521-3765</identifier><identifier>DOI: 10.1002/1521-3765(20010401)7:7<1530::AID-CHEM1530>3.0.CO;2-L</identifier><identifier>PMID: 11330909</identifier><language>eng</language><publisher>Weinheim: WILEY-VCH Verlag GmbH</publisher><subject>electron transfer ; photochemistry ; photocyclization ; phthalimide ; quantum yields</subject><ispartof>Chemistry : a European journal, 2001-04, Vol.7 (7), p.1530-1538</ispartof><rights>2001 WILEY‐VCH Verlag GmbH, Weinheim, Fed. Rep. of Germany</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2F1521-3765%2820010401%297%3A7%3C1530%3A%3AAID-CHEM1530%3E3.0.CO%3B2-L$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2F1521-3765%2820010401%297%3A7%3C1530%3A%3AAID-CHEM1530%3E3.0.CO%3B2-L$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,776,780,1411,27901,27902,45550,45551</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/11330909$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Görner, Helmut</creatorcontrib><creatorcontrib>Griesbeck, Axel G.</creatorcontrib><creatorcontrib>Heinrich, Thomas</creatorcontrib><creatorcontrib>Kramer, Wolfgang</creatorcontrib><creatorcontrib>Oelgemöller, Michael</creatorcontrib><title>Time-Resolved Spectroscopy of Sulfur- and Carboxy-Substituted N-Alkylphthalimides</title><title>Chemistry : a European journal</title><addtitle>Chem. Eur. J</addtitle><description>The photophysical and photochemical properties of N‐phthaloylmethionine (1), S‐methyl‐N‐phthaloylcysteine methyl ester (2) and N‐phthaloyltranexamic acid (3) were studied by time‐resolved UV/Vis spectroscopy, using laser pulses at 248 or 308 nm. The quantum yield of fluorescence is low (Φf<10−2) for 1–3 in fluid and glassy media, whereas that of phosphorescence is large (0.3–0.5) in ethanol at −196 °C. The triplet properties were examined in several solvents, at room temperature and below. The spectra and decay kinetics are similar, but the population of the π,π* triplet state, as measured by T–T absorption, is much lower for 1 and 2 than for 3 or N‐methyltrimellitimide (5′) at ambient temperatures. The quantum yield (ΦΔ) of singlet molecular oxygen O2(1Δg) formation is substantial for 3 and 5′ in several air‐ or oxygen‐saturated solvents at room temperature, but small for 2 and 1. The quantum yield of decomposition is substantial (0.2–0.5) for 3 and small (<0.05) for 2 and 1. It is postulated that photoinduced charge separation in the spectroscopically undetectable 3n,π* state may account for the cyclization products of 1 and 2. In aqueous solution, this also applies for 3, whereas in organic solvents cyclization involves mainly the lower lying 3π,π* state. Triplet acetone, acetophenone and xanthone are quenched by 1–3 in acetonitrile; the rate constant is close to the diffusion‐controlled limit, but smaller for benzophenone. While the energy transfer from the triplet ketone occurs for 3, a major contribution of electron transfer to the N‐phthalimide derivative is suggested for 1 and 2, where the radical anion of benzophenone or 4‐carboxybenzophenone is observed in alkaline aqueous solution.
The photophysical and photochemical properties of N‐phthaloylmethionine (1), S‐methyl‐N‐phthaloylcysteine methyl ester (2) and N‐phthaloyltranexamic acid (3) were studied by time‐resolved UV/Vis spectroscopy. The classical Kasha rule (in its photochemical version) seems to be circumvented when observing the chemical behaviour of excited 3.</description><subject>electron transfer</subject><subject>photochemistry</subject><subject>photocyclization</subject><subject>phthalimide</subject><subject>quantum yields</subject><issn>0947-6539</issn><issn>1521-3765</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2001</creationdate><recordtype>article</recordtype><recordid>eNpFkdFv0zAQxi0EYmXwL6A8IXhwOdu1HZcJqWRjndSughYQvJycxNHCkiXEyVj-exJ1LbqH09397nv4PkLOGEwZAH_PJGdUaCXfcgAGM2Dv9FyfMSlgPl9cndNoebEep49iCtNo84HT1RMyOb49JRMwM02VFOaEvPD-NwAYJcRzcsKYEGDATMiXXV46-tX5qrh3abCtXdI2lU-qug-qLNh2RdY1NLB3aRDZJq4eerrtYt_mbdcO_DVdFLd9Ud-0N7bIyzx1_iV5ltnCu1eP_ZR8-3yxi5Z0tbm8ihYrmguugSbKchNzK8Iss2HGjIuZmiltU2EkjzOd6jSRbhgYnxlgWRxKzqUSoVHKhFyckjd73bqp_nTOt1jmPnFFYe9c1XnUEDKjpRzA149gF5cuxbrJS9v0eDBhAH7ugb954fr_d8AxCBwdxdFRPASBeqjRehxywEMOKBAw2iDH1XE3aNO9du5b93DUts0tKi20xB_XlyjXn3br778ELsU_GBOOXw</recordid><startdate>20010401</startdate><enddate>20010401</enddate><creator>Görner, Helmut</creator><creator>Griesbeck, Axel G.</creator><creator>Heinrich, Thomas</creator><creator>Kramer, Wolfgang</creator><creator>Oelgemöller, Michael</creator><general>WILEY-VCH Verlag GmbH</general><general>WILEY‐VCH Verlag GmbH</general><scope>BSCLL</scope><scope>NPM</scope><scope>7X8</scope></search><sort><creationdate>20010401</creationdate><title>Time-Resolved Spectroscopy of Sulfur- and Carboxy-Substituted N-Alkylphthalimides</title><author>Görner, Helmut ; Griesbeck, Axel G. ; Heinrich, Thomas ; Kramer, Wolfgang ; Oelgemöller, Michael</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-i3270-c6a29b2a38ffa8f19eb16467ad3952bf7d7dc5e395124901fb852256389669823</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2001</creationdate><topic>electron transfer</topic><topic>photochemistry</topic><topic>photocyclization</topic><topic>phthalimide</topic><topic>quantum yields</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Görner, Helmut</creatorcontrib><creatorcontrib>Griesbeck, Axel G.</creatorcontrib><creatorcontrib>Heinrich, Thomas</creatorcontrib><creatorcontrib>Kramer, Wolfgang</creatorcontrib><creatorcontrib>Oelgemöller, Michael</creatorcontrib><collection>Istex</collection><collection>PubMed</collection><collection>MEDLINE - Academic</collection><jtitle>Chemistry : a European journal</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Görner, Helmut</au><au>Griesbeck, Axel G.</au><au>Heinrich, Thomas</au><au>Kramer, Wolfgang</au><au>Oelgemöller, Michael</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Time-Resolved Spectroscopy of Sulfur- and Carboxy-Substituted N-Alkylphthalimides</atitle><jtitle>Chemistry : a European journal</jtitle><addtitle>Chem. Eur. J</addtitle><date>2001-04-01</date><risdate>2001</risdate><volume>7</volume><issue>7</issue><spage>1530</spage><epage>1538</epage><pages>1530-1538</pages><issn>0947-6539</issn><eissn>1521-3765</eissn><abstract>The photophysical and photochemical properties of N‐phthaloylmethionine (1), S‐methyl‐N‐phthaloylcysteine methyl ester (2) and N‐phthaloyltranexamic acid (3) were studied by time‐resolved UV/Vis spectroscopy, using laser pulses at 248 or 308 nm. The quantum yield of fluorescence is low (Φf<10−2) for 1–3 in fluid and glassy media, whereas that of phosphorescence is large (0.3–0.5) in ethanol at −196 °C. The triplet properties were examined in several solvents, at room temperature and below. The spectra and decay kinetics are similar, but the population of the π,π* triplet state, as measured by T–T absorption, is much lower for 1 and 2 than for 3 or N‐methyltrimellitimide (5′) at ambient temperatures. The quantum yield (ΦΔ) of singlet molecular oxygen O2(1Δg) formation is substantial for 3 and 5′ in several air‐ or oxygen‐saturated solvents at room temperature, but small for 2 and 1. The quantum yield of decomposition is substantial (0.2–0.5) for 3 and small (<0.05) for 2 and 1. It is postulated that photoinduced charge separation in the spectroscopically undetectable 3n,π* state may account for the cyclization products of 1 and 2. In aqueous solution, this also applies for 3, whereas in organic solvents cyclization involves mainly the lower lying 3π,π* state. Triplet acetone, acetophenone and xanthone are quenched by 1–3 in acetonitrile; the rate constant is close to the diffusion‐controlled limit, but smaller for benzophenone. While the energy transfer from the triplet ketone occurs for 3, a major contribution of electron transfer to the N‐phthalimide derivative is suggested for 1 and 2, where the radical anion of benzophenone or 4‐carboxybenzophenone is observed in alkaline aqueous solution.
The photophysical and photochemical properties of N‐phthaloylmethionine (1), S‐methyl‐N‐phthaloylcysteine methyl ester (2) and N‐phthaloyltranexamic acid (3) were studied by time‐resolved UV/Vis spectroscopy. The classical Kasha rule (in its photochemical version) seems to be circumvented when observing the chemical behaviour of excited 3.</abstract><cop>Weinheim</cop><pub>WILEY-VCH Verlag GmbH</pub><pmid>11330909</pmid><doi>10.1002/1521-3765(20010401)7:7<1530::AID-CHEM1530>3.0.CO;2-L</doi><tpages>9</tpages></addata></record> |
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| subjects | electron transfer photochemistry photocyclization phthalimide quantum yields |
| title | Time-Resolved Spectroscopy of Sulfur- and Carboxy-Substituted N-Alkylphthalimides |
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