Influence of molecular distortion on the exciton quenching for quaterthiophene-terminated self-assembled monolayers on Au(111)
•We found n-parity-dependent lifetime τ for photoexcited 4T-(CH2)nS-SAMs on gold.•Independent of n, the quenching is due to an excitation energy transfer mechanism.•The n parity dependence of τ results from conformation change of -(CH2)nS- chains.•Importance of molecular design even in aliphatic par...
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| Veröffentlicht in: | Surface science 2018-03, Vol.669, p.160-168 |
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| creator | Kato, Hiroyuki S. Murakami, Yoshinari Saitoh, Riyo Osumi, Yuji Okaue, Daijiro Kiriyama, Yoshiaki Ueba, Takahiro Yamada, Takashi Ie, Yutaka Aso, Yoshio Munakata, Toshiaki |
| description | •We found n-parity-dependent lifetime τ for photoexcited 4T-(CH2)nS-SAMs on gold.•Independent of n, the quenching is due to an excitation energy transfer mechanism.•The n parity dependence of τ results from conformation change of -(CH2)nS- chains.•Importance of molecular design even in aliphatic parts for organic device is shown.
We have studied the dynamics of photoexcited electronic states for structure-specific alkanethiolate-based self-assembled monolayers (SAMs) on Au(111). At the even numbers of methylene units (n) in the alkylene chain, a molecular distortion due to strong interference between the end substituents is expected. Focused on this geometrical perturbation, here, we examine the influence of the molecular distortion on the quenching process of photoexcited quaterthiophene (4T)-terminated alkanethiolate SAMs (4TCnS-SAMs) for even n (= 6 and 8). The occupied and unoccupied electronic levels of 4TCnS-SAMs are specified by ultraviolet photoelectron spectroscopy (UPS) and two-photon photoemission (2PPE) spectroscopy, respectively. The quenching rate, i.e., lifetime (τn), of the photoexcited state for 4TCnS-SAMs is evaluated by the time-resolved 2PPE measurements. In comparison to the previously reported results for odd n [J. Phys. Chem. C 119 (2015) 7400–7407], we find that τn for even n is not in the middle of those for n ± 1 but close to that for n − 1, i.e., τ6 ≈ τ5 and τ8 ≈ τ7, in contrast to the negligible difference in the electronic levels for all n. By the examination of molecular configurations using scanning tunneling microscopy (STM) and infrared reflection absorption spectroscopy (IRAS), we elucidate the weak n dependence of the 4T group orientation and the n-parity-dependent conformation change of alkylene chain. We conclude that the n parity dependence of τn results from a structural distortion of the aliphatic alkylene chain, in which a skewed alkylene chain appears for even n, rather than the electronic modification of the aromatic 4T groups.
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| doi_str_mv | 10.1016/j.susc.2017.11.014 |
| format | Article |
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We have studied the dynamics of photoexcited electronic states for structure-specific alkanethiolate-based self-assembled monolayers (SAMs) on Au(111). At the even numbers of methylene units (n) in the alkylene chain, a molecular distortion due to strong interference between the end substituents is expected. Focused on this geometrical perturbation, here, we examine the influence of the molecular distortion on the quenching process of photoexcited quaterthiophene (4T)-terminated alkanethiolate SAMs (4TCnS-SAMs) for even n (= 6 and 8). The occupied and unoccupied electronic levels of 4TCnS-SAMs are specified by ultraviolet photoelectron spectroscopy (UPS) and two-photon photoemission (2PPE) spectroscopy, respectively. The quenching rate, i.e., lifetime (τn), of the photoexcited state for 4TCnS-SAMs is evaluated by the time-resolved 2PPE measurements. In comparison to the previously reported results for odd n [J. Phys. Chem. C 119 (2015) 7400–7407], we find that τn for even n is not in the middle of those for n ± 1 but close to that for n − 1, i.e., τ6 ≈ τ5 and τ8 ≈ τ7, in contrast to the negligible difference in the electronic levels for all n. By the examination of molecular configurations using scanning tunneling microscopy (STM) and infrared reflection absorption spectroscopy (IRAS), we elucidate the weak n dependence of the 4T group orientation and the n-parity-dependent conformation change of alkylene chain. We conclude that the n parity dependence of τn results from a structural distortion of the aliphatic alkylene chain, in which a skewed alkylene chain appears for even n, rather than the electronic modification of the aromatic 4T groups.
[Display omitted]</description><identifier>ISSN: 0039-6028</identifier><identifier>EISSN: 1879-2758</identifier><identifier>DOI: 10.1016/j.susc.2017.11.014</identifier><language>eng</language><publisher>Amsterdam: Elsevier B.V</publisher><subject>Aliphatic compounds ; Alkanes ; Chains ; Dependence ; Distortion ; Dynamic structural analysis ; Electron states ; Excitation energy transfer process ; Functional SAM ; Gas absorption ; Gold ; HOMO-LUMO transition ; Infrared reflection ; Molecular chains ; Molecular conformation ; Monolayers ; Odd-Even effect ; Oligothiophene ; Parity ; Photoelectric emission ; Quenching ; Scanning electron microscopy ; Self-assembled monolayers ; Self-assembly ; Spectrum analysis</subject><ispartof>Surface science, 2018-03, Vol.669, p.160-168</ispartof><rights>2017 Elsevier B.V.</rights><rights>Copyright Elsevier BV Mar 2018</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c394t-5d2c45a91f2dadc255bc49b6a87d55a6d84750560c7fa41543b80bb6a0ad37be3</citedby><cites>FETCH-LOGICAL-c394t-5d2c45a91f2dadc255bc49b6a87d55a6d84750560c7fa41543b80bb6a0ad37be3</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktohtml>$$Uhttps://dx.doi.org/10.1016/j.susc.2017.11.014$$EHTML$$P50$$Gelsevier$$H</linktohtml><link.rule.ids>314,780,784,3550,27924,27925,45995</link.rule.ids></links><search><creatorcontrib>Kato, Hiroyuki S.</creatorcontrib><creatorcontrib>Murakami, Yoshinari</creatorcontrib><creatorcontrib>Saitoh, Riyo</creatorcontrib><creatorcontrib>Osumi, Yuji</creatorcontrib><creatorcontrib>Okaue, Daijiro</creatorcontrib><creatorcontrib>Kiriyama, Yoshiaki</creatorcontrib><creatorcontrib>Ueba, Takahiro</creatorcontrib><creatorcontrib>Yamada, Takashi</creatorcontrib><creatorcontrib>Ie, Yutaka</creatorcontrib><creatorcontrib>Aso, Yoshio</creatorcontrib><creatorcontrib>Munakata, Toshiaki</creatorcontrib><title>Influence of molecular distortion on the exciton quenching for quaterthiophene-terminated self-assembled monolayers on Au(111)</title><title>Surface science</title><description>•We found n-parity-dependent lifetime τ for photoexcited 4T-(CH2)nS-SAMs on gold.•Independent of n, the quenching is due to an excitation energy transfer mechanism.•The n parity dependence of τ results from conformation change of -(CH2)nS- chains.•Importance of molecular design even in aliphatic parts for organic device is shown.
We have studied the dynamics of photoexcited electronic states for structure-specific alkanethiolate-based self-assembled monolayers (SAMs) on Au(111). At the even numbers of methylene units (n) in the alkylene chain, a molecular distortion due to strong interference between the end substituents is expected. Focused on this geometrical perturbation, here, we examine the influence of the molecular distortion on the quenching process of photoexcited quaterthiophene (4T)-terminated alkanethiolate SAMs (4TCnS-SAMs) for even n (= 6 and 8). The occupied and unoccupied electronic levels of 4TCnS-SAMs are specified by ultraviolet photoelectron spectroscopy (UPS) and two-photon photoemission (2PPE) spectroscopy, respectively. The quenching rate, i.e., lifetime (τn), of the photoexcited state for 4TCnS-SAMs is evaluated by the time-resolved 2PPE measurements. In comparison to the previously reported results for odd n [J. Phys. Chem. C 119 (2015) 7400–7407], we find that τn for even n is not in the middle of those for n ± 1 but close to that for n − 1, i.e., τ6 ≈ τ5 and τ8 ≈ τ7, in contrast to the negligible difference in the electronic levels for all n. By the examination of molecular configurations using scanning tunneling microscopy (STM) and infrared reflection absorption spectroscopy (IRAS), we elucidate the weak n dependence of the 4T group orientation and the n-parity-dependent conformation change of alkylene chain. We conclude that the n parity dependence of τn results from a structural distortion of the aliphatic alkylene chain, in which a skewed alkylene chain appears for even n, rather than the electronic modification of the aromatic 4T groups.
[Display omitted]</description><subject>Aliphatic compounds</subject><subject>Alkanes</subject><subject>Chains</subject><subject>Dependence</subject><subject>Distortion</subject><subject>Dynamic structural analysis</subject><subject>Electron states</subject><subject>Excitation energy transfer process</subject><subject>Functional SAM</subject><subject>Gas absorption</subject><subject>Gold</subject><subject>HOMO-LUMO transition</subject><subject>Infrared reflection</subject><subject>Molecular chains</subject><subject>Molecular conformation</subject><subject>Monolayers</subject><subject>Odd-Even effect</subject><subject>Oligothiophene</subject><subject>Parity</subject><subject>Photoelectric emission</subject><subject>Quenching</subject><subject>Scanning electron microscopy</subject><subject>Self-assembled monolayers</subject><subject>Self-assembly</subject><subject>Spectrum analysis</subject><issn>0039-6028</issn><issn>1879-2758</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2018</creationdate><recordtype>article</recordtype><recordid>eNp9kEtPxCAUhYnRxHH0D7hq4kYXrUChj8TNZOJjkknc6JpQuLVM2jICNc7G3y7NuJaQcA-cc4EPoWuCM4JJcb_L_ORVRjEpM0IyTNgJWpCqrFNa8uoULTDO67TAtDpHF97vcBys5gv0sxnbfoJRQWLbZLA9qKmXLtHGB-uCsWMSZ-gggW9lQqw_Z3dnxo-ktS4qGcCFzth9ByOkUQxmjHs68dC3qfQehqaPcrCj7eUBnJ87rqZbQsjdJTprZe_h6m9dovenx7f1S7p9fd6sV9tU5TULKddUMS5r0lIttaKcN4rVTSGrUnMuC12xkmNeYFW2khHO8qbCTTzHUudlA_kS3Rz77p2NH_BB7OzkxniloLjglFNas-iiR5dy1nsHrdg7M0h3EASLmbPYiZmzmDkLQkTkHEMPxxDE938ZcMIrMwPVxoEKQlvzX_wXdRSJGQ</recordid><startdate>201803</startdate><enddate>201803</enddate><creator>Kato, Hiroyuki S.</creator><creator>Murakami, Yoshinari</creator><creator>Saitoh, Riyo</creator><creator>Osumi, Yuji</creator><creator>Okaue, Daijiro</creator><creator>Kiriyama, Yoshiaki</creator><creator>Ueba, Takahiro</creator><creator>Yamada, Takashi</creator><creator>Ie, Yutaka</creator><creator>Aso, Yoshio</creator><creator>Munakata, Toshiaki</creator><general>Elsevier B.V</general><general>Elsevier BV</general><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>7U5</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>L7M</scope></search><sort><creationdate>201803</creationdate><title>Influence of molecular distortion on the exciton quenching for quaterthiophene-terminated self-assembled monolayers on Au(111)</title><author>Kato, Hiroyuki S. ; Murakami, Yoshinari ; Saitoh, Riyo ; Osumi, Yuji ; Okaue, Daijiro ; Kiriyama, Yoshiaki ; Ueba, Takahiro ; Yamada, Takashi ; Ie, Yutaka ; Aso, Yoshio ; Munakata, Toshiaki</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c394t-5d2c45a91f2dadc255bc49b6a87d55a6d84750560c7fa41543b80bb6a0ad37be3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2018</creationdate><topic>Aliphatic compounds</topic><topic>Alkanes</topic><topic>Chains</topic><topic>Dependence</topic><topic>Distortion</topic><topic>Dynamic structural analysis</topic><topic>Electron states</topic><topic>Excitation energy transfer process</topic><topic>Functional SAM</topic><topic>Gas absorption</topic><topic>Gold</topic><topic>HOMO-LUMO transition</topic><topic>Infrared reflection</topic><topic>Molecular chains</topic><topic>Molecular conformation</topic><topic>Monolayers</topic><topic>Odd-Even effect</topic><topic>Oligothiophene</topic><topic>Parity</topic><topic>Photoelectric emission</topic><topic>Quenching</topic><topic>Scanning electron microscopy</topic><topic>Self-assembled monolayers</topic><topic>Self-assembly</topic><topic>Spectrum analysis</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Kato, Hiroyuki S.</creatorcontrib><creatorcontrib>Murakami, Yoshinari</creatorcontrib><creatorcontrib>Saitoh, Riyo</creatorcontrib><creatorcontrib>Osumi, Yuji</creatorcontrib><creatorcontrib>Okaue, Daijiro</creatorcontrib><creatorcontrib>Kiriyama, Yoshiaki</creatorcontrib><creatorcontrib>Ueba, Takahiro</creatorcontrib><creatorcontrib>Yamada, Takashi</creatorcontrib><creatorcontrib>Ie, Yutaka</creatorcontrib><creatorcontrib>Aso, Yoshio</creatorcontrib><creatorcontrib>Munakata, Toshiaki</creatorcontrib><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>Advanced Technologies Database with Aerospace</collection><jtitle>Surface science</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Kato, Hiroyuki S.</au><au>Murakami, Yoshinari</au><au>Saitoh, Riyo</au><au>Osumi, Yuji</au><au>Okaue, Daijiro</au><au>Kiriyama, Yoshiaki</au><au>Ueba, Takahiro</au><au>Yamada, Takashi</au><au>Ie, Yutaka</au><au>Aso, Yoshio</au><au>Munakata, Toshiaki</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Influence of molecular distortion on the exciton quenching for quaterthiophene-terminated self-assembled monolayers on Au(111)</atitle><jtitle>Surface science</jtitle><date>2018-03</date><risdate>2018</risdate><volume>669</volume><spage>160</spage><epage>168</epage><pages>160-168</pages><issn>0039-6028</issn><eissn>1879-2758</eissn><abstract>•We found n-parity-dependent lifetime τ for photoexcited 4T-(CH2)nS-SAMs on gold.•Independent of n, the quenching is due to an excitation energy transfer mechanism.•The n parity dependence of τ results from conformation change of -(CH2)nS- chains.•Importance of molecular design even in aliphatic parts for organic device is shown.
We have studied the dynamics of photoexcited electronic states for structure-specific alkanethiolate-based self-assembled monolayers (SAMs) on Au(111). At the even numbers of methylene units (n) in the alkylene chain, a molecular distortion due to strong interference between the end substituents is expected. Focused on this geometrical perturbation, here, we examine the influence of the molecular distortion on the quenching process of photoexcited quaterthiophene (4T)-terminated alkanethiolate SAMs (4TCnS-SAMs) for even n (= 6 and 8). The occupied and unoccupied electronic levels of 4TCnS-SAMs are specified by ultraviolet photoelectron spectroscopy (UPS) and two-photon photoemission (2PPE) spectroscopy, respectively. The quenching rate, i.e., lifetime (τn), of the photoexcited state for 4TCnS-SAMs is evaluated by the time-resolved 2PPE measurements. In comparison to the previously reported results for odd n [J. Phys. Chem. C 119 (2015) 7400–7407], we find that τn for even n is not in the middle of those for n ± 1 but close to that for n − 1, i.e., τ6 ≈ τ5 and τ8 ≈ τ7, in contrast to the negligible difference in the electronic levels for all n. By the examination of molecular configurations using scanning tunneling microscopy (STM) and infrared reflection absorption spectroscopy (IRAS), we elucidate the weak n dependence of the 4T group orientation and the n-parity-dependent conformation change of alkylene chain. We conclude that the n parity dependence of τn results from a structural distortion of the aliphatic alkylene chain, in which a skewed alkylene chain appears for even n, rather than the electronic modification of the aromatic 4T groups.
[Display omitted]</abstract><cop>Amsterdam</cop><pub>Elsevier B.V</pub><doi>10.1016/j.susc.2017.11.014</doi><tpages>9</tpages></addata></record> |
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| subjects | Aliphatic compounds Alkanes Chains Dependence Distortion Dynamic structural analysis Electron states Excitation energy transfer process Functional SAM Gas absorption Gold HOMO-LUMO transition Infrared reflection Molecular chains Molecular conformation Monolayers Odd-Even effect Oligothiophene Parity Photoelectric emission Quenching Scanning electron microscopy Self-assembled monolayers Self-assembly Spectrum analysis |
| title | Influence of molecular distortion on the exciton quenching for quaterthiophene-terminated self-assembled monolayers on Au(111) |
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