Luminescent Ce(III) Complexes as Stoichiometric and Catalytic Photoreductants for Halogen Atom Abstraction Reactions
Luminescent Ce(III) complexes, Ce[N(SiMe3)2]3 (1) and [(Me3Si)2NC(RN)2]Ce[N(SiMe3)2]2 (R = i Pr, 1- i Pr; R = Cy, 1-Cy), with C 3v and C 2v solution symmetries display absorptive 4f → 5d electronic transitions in the visible region. Emission bands are observed at 553, 518, and 523 nm for 1, 1...
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| Veröffentlicht in: | Journal of the American Chemical Society 2015-07, Vol.137 (29), p.9234-9237 |
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| container_title | Journal of the American Chemical Society |
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| creator | Yin, Haolin Carroll, Patrick J Anna, Jessica M Schelter, Eric J |
| description | Luminescent Ce(III) complexes, Ce[N(SiMe3)2]3 (1) and [(Me3Si)2NC(RN)2]Ce[N(SiMe3)2]2 (R = i Pr, 1- i Pr; R = Cy, 1-Cy), with C 3v and C 2v solution symmetries display absorptive 4f → 5d electronic transitions in the visible region. Emission bands are observed at 553, 518, and 523 nm for 1, 1- i Pr, and 1-Cy with lifetimes of 24, 67, and 61 ns, respectively. Time-dependent density functional theory (TD-DFT) studies on 1 and 1- i Pr revealed the 2A1 excited states corresponded to singly occupied 5d z 2 orbitals. The strongly reducing metalloradical character of 1, 1- i Pr, and 1-Cy in their 2A1 excited states afforded photochemical halogen atom abstraction reactions from sp3 and sp2 C–X (X = Cl, Br, I) bonds for the first time with a lanthanide cation. The dehalogenation reactions could be turned over with catalytic amounts of photosensitizers by coupling salt metathesis and reduction to the photopromoted atom abstraction reactions. |
| doi_str_mv | 10.1021/jacs.5b05411 |
| format | Article |
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Emission bands are observed at 553, 518, and 523 nm for 1, 1- i Pr, and 1-Cy with lifetimes of 24, 67, and 61 ns, respectively. Time-dependent density functional theory (TD-DFT) studies on 1 and 1- i Pr revealed the 2A1 excited states corresponded to singly occupied 5d z 2 orbitals. The strongly reducing metalloradical character of 1, 1- i Pr, and 1-Cy in their 2A1 excited states afforded photochemical halogen atom abstraction reactions from sp3 and sp2 C–X (X = Cl, Br, I) bonds for the first time with a lanthanide cation. The dehalogenation reactions could be turned over with catalytic amounts of photosensitizers by coupling salt metathesis and reduction to the photopromoted atom abstraction reactions.</description><identifier>ISSN: 0002-7863</identifier><identifier>EISSN: 1520-5126</identifier><identifier>DOI: 10.1021/jacs.5b05411</identifier><identifier>PMID: 26151154</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><ispartof>Journal of the American Chemical Society, 2015-07, Vol.137 (29), p.9234-9237</ispartof><rights>Copyright © 2015 American Chemical Society</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a362t-a385606502e1c65ff30a5d583b0e530705c4e6556e89f2284876386f79e823b73</citedby><cites>FETCH-LOGICAL-a362t-a385606502e1c65ff30a5d583b0e530705c4e6556e89f2284876386f79e823b73</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/jacs.5b05411$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/jacs.5b05411$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,776,780,2752,27053,27901,27902,56713,56763</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/26151154$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Yin, Haolin</creatorcontrib><creatorcontrib>Carroll, Patrick J</creatorcontrib><creatorcontrib>Anna, Jessica M</creatorcontrib><creatorcontrib>Schelter, Eric J</creatorcontrib><title>Luminescent Ce(III) Complexes as Stoichiometric and Catalytic Photoreductants for Halogen Atom Abstraction Reactions</title><title>Journal of the American Chemical Society</title><addtitle>J. Am. Chem. Soc</addtitle><description>Luminescent Ce(III) complexes, Ce[N(SiMe3)2]3 (1) and [(Me3Si)2NC(RN)2]Ce[N(SiMe3)2]2 (R = i Pr, 1- i Pr; R = Cy, 1-Cy), with C 3v and C 2v solution symmetries display absorptive 4f → 5d electronic transitions in the visible region. Emission bands are observed at 553, 518, and 523 nm for 1, 1- i Pr, and 1-Cy with lifetimes of 24, 67, and 61 ns, respectively. Time-dependent density functional theory (TD-DFT) studies on 1 and 1- i Pr revealed the 2A1 excited states corresponded to singly occupied 5d z 2 orbitals. The strongly reducing metalloradical character of 1, 1- i Pr, and 1-Cy in their 2A1 excited states afforded photochemical halogen atom abstraction reactions from sp3 and sp2 C–X (X = Cl, Br, I) bonds for the first time with a lanthanide cation. 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Am. Chem. Soc</addtitle><date>2015-07-29</date><risdate>2015</risdate><volume>137</volume><issue>29</issue><spage>9234</spage><epage>9237</epage><pages>9234-9237</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><abstract>Luminescent Ce(III) complexes, Ce[N(SiMe3)2]3 (1) and [(Me3Si)2NC(RN)2]Ce[N(SiMe3)2]2 (R = i Pr, 1- i Pr; R = Cy, 1-Cy), with C 3v and C 2v solution symmetries display absorptive 4f → 5d electronic transitions in the visible region. Emission bands are observed at 553, 518, and 523 nm for 1, 1- i Pr, and 1-Cy with lifetimes of 24, 67, and 61 ns, respectively. Time-dependent density functional theory (TD-DFT) studies on 1 and 1- i Pr revealed the 2A1 excited states corresponded to singly occupied 5d z 2 orbitals. The strongly reducing metalloradical character of 1, 1- i Pr, and 1-Cy in their 2A1 excited states afforded photochemical halogen atom abstraction reactions from sp3 and sp2 C–X (X = Cl, Br, I) bonds for the first time with a lanthanide cation. The dehalogenation reactions could be turned over with catalytic amounts of photosensitizers by coupling salt metathesis and reduction to the photopromoted atom abstraction reactions.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>26151154</pmid><doi>10.1021/jacs.5b05411</doi><tpages>4</tpages><oa>free_for_read</oa></addata></record> |
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| title | Luminescent Ce(III) Complexes as Stoichiometric and Catalytic Photoreductants for Halogen Atom Abstraction Reactions |
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