Force-induced tautomerization in a single molecule
Heat transfer, electrical potential and light energy are common ways to activate chemical reactions. Applied force is another way, but dedicated studies for such a mechanical activation are limited, and this activation is poorly understood at the single-molecule level. Here, we report force-induced...
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| Veröffentlicht in: | Nature chemistry 2016-10, Vol.8 (10), p.935-940 |
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| creator | Ladenthin, Janina N. Frederiksen, Thomas Persson, Mats Sharp, John C. Gawinkowski, Sylwester Waluk, Jacek Kumagai, Takashi |
| description | Heat transfer, electrical potential and light energy are common ways to activate chemical reactions. Applied force is another way, but dedicated studies for such a mechanical activation are limited, and this activation is poorly understood at the single-molecule level. Here, we report force-induced tautomerization in a single porphycene molecule on a Cu(110) surface at 5 K, which is studied by scanning probe microscopy and density functional theory calculations. Force spectroscopy quantifies the force needed to trigger tautomerization with submolecular spatial resolution. The calculations show how the reaction pathway and barrier of tautomerization are modified in the presence of a copper tip and reveal the atomistic origin of the process. Moreover, we demonstrate that a chemically inert tip whose apex is terminated by a xenon atom cannot induce the reaction because of a weak interaction with porphycene and a strong relaxation of xenon on the tip as contact to the molecule is formed.
Force-induced tautomerization in a single porphycene molecule is investigated on a Cu(110) surface at 5 K by using non-contact atomic force microscopy. The force needed to trigger the tautomerization process is quantified by force spectroscopy and theoretical calculations reveal the atomistic mechanism behind the reaction. |
| doi_str_mv | 10.1038/nchem.2552 |
| format | Article |
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Force-induced tautomerization in a single porphycene molecule is investigated on a Cu(110) surface at 5 K by using non-contact atomic force microscopy. The force needed to trigger the tautomerization process is quantified by force spectroscopy and theoretical calculations reveal the atomistic mechanism behind the reaction.</description><identifier>ISSN: 1755-4330</identifier><identifier>EISSN: 1755-4349</identifier><identifier>DOI: 10.1038/nchem.2552</identifier><identifier>PMID: 27657869</identifier><language>eng</language><publisher>London: Nature Publishing Group UK</publisher><subject>119/118 ; 147/138 ; 147/3 ; 639/638/542 ; 639/638/542/968 ; 639/925 ; Analytical Chemistry ; Biochemistry ; Chemical bonds ; Chemical reactions ; Chemistry ; Chemistry/Food Science ; Electrons ; Heat transfer ; Hydrogen ; Inorganic Chemistry ; Microscopy ; Organic Chemistry ; Physical Chemistry ; Science ; Xenon</subject><ispartof>Nature chemistry, 2016-10, Vol.8 (10), p.935-940</ispartof><rights>Springer Nature Limited 2016</rights><rights>Copyright Nature Publishing Group Oct 2016</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c487t-46c34b9c9666f5c470b8ca90b57892841bb5945ad72fa3a89e1e08891317e2193</citedby><cites>FETCH-LOGICAL-c487t-46c34b9c9666f5c470b8ca90b57892841bb5945ad72fa3a89e1e08891317e2193</cites><orcidid>0000-0001-7523-7641</orcidid></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/27657869$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Ladenthin, Janina N.</creatorcontrib><creatorcontrib>Frederiksen, Thomas</creatorcontrib><creatorcontrib>Persson, Mats</creatorcontrib><creatorcontrib>Sharp, John C.</creatorcontrib><creatorcontrib>Gawinkowski, Sylwester</creatorcontrib><creatorcontrib>Waluk, Jacek</creatorcontrib><creatorcontrib>Kumagai, Takashi</creatorcontrib><title>Force-induced tautomerization in a single molecule</title><title>Nature chemistry</title><addtitle>Nature Chem</addtitle><addtitle>Nat Chem</addtitle><description>Heat transfer, electrical potential and light energy are common ways to activate chemical reactions. Applied force is another way, but dedicated studies for such a mechanical activation are limited, and this activation is poorly understood at the single-molecule level. Here, we report force-induced tautomerization in a single porphycene molecule on a Cu(110) surface at 5 K, which is studied by scanning probe microscopy and density functional theory calculations. Force spectroscopy quantifies the force needed to trigger tautomerization with submolecular spatial resolution. The calculations show how the reaction pathway and barrier of tautomerization are modified in the presence of a copper tip and reveal the atomistic origin of the process. Moreover, we demonstrate that a chemically inert tip whose apex is terminated by a xenon atom cannot induce the reaction because of a weak interaction with porphycene and a strong relaxation of xenon on the tip as contact to the molecule is formed.
Force-induced tautomerization in a single porphycene molecule is investigated on a Cu(110) surface at 5 K by using non-contact atomic force microscopy. 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Force-induced tautomerization in a single porphycene molecule is investigated on a Cu(110) surface at 5 K by using non-contact atomic force microscopy. The force needed to trigger the tautomerization process is quantified by force spectroscopy and theoretical calculations reveal the atomistic mechanism behind the reaction.</abstract><cop>London</cop><pub>Nature Publishing Group UK</pub><pmid>27657869</pmid><doi>10.1038/nchem.2552</doi><tpages>6</tpages><orcidid>https://orcid.org/0000-0001-7523-7641</orcidid></addata></record> |
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| subjects | 119/118 147/138 147/3 639/638/542 639/638/542/968 639/925 Analytical Chemistry Biochemistry Chemical bonds Chemical reactions Chemistry Chemistry/Food Science Electrons Heat transfer Hydrogen Inorganic Chemistry Microscopy Organic Chemistry Physical Chemistry Science Xenon |
| title | Force-induced tautomerization in a single molecule |
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