Synthesis, Linear, and Quadratic-Nonlinear Optical Properties of Octupolar D3 and D2d Bipyridyl Metal Complexes
A series of D3 (FeII, RuII, ZnII, HgII) and D2d (CuI, AgI, ZnII) octupolar metal complexes featuring different functionalized bipyridyl ligands has been synthesized, and their thermal, linear (absorption and emission), and nonlinear optical (NLO) properties were determined. Their quadratic NLO susce...
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| Veröffentlicht in: | Chemistry : a European journal 2004-09, Vol.10 (18), p.4454-4466 |
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| creator | Maury, Olivier Viau, Lydie Sénéchal, Katell Corre, Brigitte Guégan, Jean-Paul Renouard, Thierry Ledoux, Isabelle Zyss, Joseph Le Bozec, Hubert |
| description | A series of D3 (FeII, RuII, ZnII, HgII) and D2d (CuI, AgI, ZnII) octupolar metal complexes featuring different functionalized bipyridyl ligands has been synthesized, and their thermal, linear (absorption and emission), and nonlinear optical (NLO) properties were determined. Their quadratic NLO susceptibilities were determined by harmonic light scattering at 1.91 μm, and the molecular hyperpolarizability (β0) values are in the range of 200–657×10−30 esu for octahedral complexes and 70–157×10−30 esu for tetrahedral complexes. The octahedral zinc(II) complex 1 e, which contains a 4,4′‐oligophenylenevinylene‐functionalized 2,2′‐bipyridine, exhibits the highest quadratic hyperpolarizability ever reported for an octupolar derivative (λmax=482 nm, β1.91(1 e)=870×10−30 esu, β0(1 e)=657×10−30 esu). Herein, we demonstrate that the optical and nonlinear optical (NLO) properties are strongly influenced by the symmetry of the complexes, the nature of the ligands (donor endgroups and π linkers), and the nature of the metallic centers. For example, the length of the π‐conjugated backbone, the Lewis acidity of the metal ion, and the increase of ligand‐to‐metal ratio result in a substantial enhancement of β. The contribution of the metal‐to‐ligand (MLCT) transition to the molecular hyperpolarizability is also discussed with respect to octahedral d6 complexes (M=Fe, Ru).
Sintezekaet zo bet ur familh kemplezhioù metalek eizhpol, enno ligantoù daoubiridin arc'hwelekaet. O ferzhioù termek, optik linennek (euvriñ ha skingas) hag anlinennek zo bet termenet. Oberiegezh optikel anlinennek ar c'hediadoù‐se zo bet gallet termeniñ gant teknik skignañ harmonek ar sklêrijenn diouzh un hirder gwagennoù a 1.91 μm: talvoudegezhioù arβ0 zo etre 200 ha 657×10−30 ues evit ar c'hemplezhioù eizhtalek hag etre 70 ha 157×10−30 ues evit ar c'hemplezhioù pevarzalek. Gant ar c'hediad zink(II) 1 añ emañ an oberiegezh anlinennek eil‐urzh kreñvañ a vefe bet a‐viskoazh evit ur volekulenn eizhpol. Gant ar studiadenn‐mañ eo sklaer pegen levezonet eo ar perzhioù optik linennek hag anlinennek gant simetriezh ar molekul, anien al ligantoù (anien ar roer hag ar reizhiad treuzkas) hag anien ar c'hreiz metalek. Da skouer, gant hirder ar chadenn kediet, trenkted Lewis ar metal ha kresk ar c'heñver ligant/metal e kresk kalz ar β0. Mod‐all ez eus bet lakaet sklaer e ro an MLCT harp d'an oberiegezh optik anlinennek er c'hemplezhioù eizhtalek d6.
A series of D3 and D2d octupolar metal complexes, namely tris(bipyrid |
| doi_str_mv | 10.1002/chem.200400012 |
| format | Article |
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Sintezekaet zo bet ur familh kemplezhioù metalek eizhpol, enno ligantoù daoubiridin arc'hwelekaet. O ferzhioù termek, optik linennek (euvriñ ha skingas) hag anlinennek zo bet termenet. Oberiegezh optikel anlinennek ar c'hediadoù‐se zo bet gallet termeniñ gant teknik skignañ harmonek ar sklêrijenn diouzh un hirder gwagennoù a 1.91 μm: talvoudegezhioù arβ0 zo etre 200 ha 657×10−30 ues evit ar c'hemplezhioù eizhtalek hag etre 70 ha 157×10−30 ues evit ar c'hemplezhioù pevarzalek. Gant ar c'hediad zink(II) 1 añ emañ an oberiegezh anlinennek eil‐urzh kreñvañ a vefe bet a‐viskoazh evit ur volekulenn eizhpol. Gant ar studiadenn‐mañ eo sklaer pegen levezonet eo ar perzhioù optik linennek hag anlinennek gant simetriezh ar molekul, anien al ligantoù (anien ar roer hag ar reizhiad treuzkas) hag anien ar c'hreiz metalek. Da skouer, gant hirder ar chadenn kediet, trenkted Lewis ar metal ha kresk ar c'heñver ligant/metal e kresk kalz ar β0. Mod‐all ez eus bet lakaet sklaer e ro an MLCT harp d'an oberiegezh optik anlinennek er c'hemplezhioù eizhtalek d6.
A series of D3 and D2d octupolar metal complexes, namely tris(bipyridyl)metal complexes (FeII, RuII, ZnII, HgII) and bis(bipyridyl)metal complexes (CuI, AgI, ZnII), featuring different functionalized bipyridyl ligands were prepared, an example of which is shown here. Their optical and nonlinear optical (NLO) properties are strongly influenced by the symmetry of the complexes, the nature of the ligands (donor endgroups and π linkers), and the nature of the metallic centers.</description><identifier>ISSN: 0947-6539</identifier><identifier>EISSN: 1521-3765</identifier><identifier>DOI: 10.1002/chem.200400012</identifier><identifier>PMID: 15378623</identifier><language>eng</language><publisher>Weinheim: WILEY-VCH Verlag</publisher><subject>2,2'-Dipyridyl - chemistry ; absorption ; coordination chemistry ; fluorescence ; ligand design ; Metals, Heavy - chemistry ; Molecular Structure ; N ligands ; nonlinear optics ; Organometallic Compounds - chemical synthesis ; Organometallic Compounds - chemistry</subject><ispartof>Chemistry : a European journal, 2004-09, Vol.10 (18), p.4454-4466</ispartof><rights>Copyright © 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim</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%2Fchem.200400012$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fchem.200400012$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,780,784,1417,27924,27925,45574,45575</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/15378623$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Maury, Olivier</creatorcontrib><creatorcontrib>Viau, Lydie</creatorcontrib><creatorcontrib>Sénéchal, Katell</creatorcontrib><creatorcontrib>Corre, Brigitte</creatorcontrib><creatorcontrib>Guégan, Jean-Paul</creatorcontrib><creatorcontrib>Renouard, Thierry</creatorcontrib><creatorcontrib>Ledoux, Isabelle</creatorcontrib><creatorcontrib>Zyss, Joseph</creatorcontrib><creatorcontrib>Le Bozec, Hubert</creatorcontrib><title>Synthesis, Linear, and Quadratic-Nonlinear Optical Properties of Octupolar D3 and D2d Bipyridyl Metal Complexes</title><title>Chemistry : a European journal</title><addtitle>Chemistry - A European Journal</addtitle><description>A series of D3 (FeII, RuII, ZnII, HgII) and D2d (CuI, AgI, ZnII) octupolar metal complexes featuring different functionalized bipyridyl ligands has been synthesized, and their thermal, linear (absorption and emission), and nonlinear optical (NLO) properties were determined. Their quadratic NLO susceptibilities were determined by harmonic light scattering at 1.91 μm, and the molecular hyperpolarizability (β0) values are in the range of 200–657×10−30 esu for octahedral complexes and 70–157×10−30 esu for tetrahedral complexes. The octahedral zinc(II) complex 1 e, which contains a 4,4′‐oligophenylenevinylene‐functionalized 2,2′‐bipyridine, exhibits the highest quadratic hyperpolarizability ever reported for an octupolar derivative (λmax=482 nm, β1.91(1 e)=870×10−30 esu, β0(1 e)=657×10−30 esu). Herein, we demonstrate that the optical and nonlinear optical (NLO) properties are strongly influenced by the symmetry of the complexes, the nature of the ligands (donor endgroups and π linkers), and the nature of the metallic centers. For example, the length of the π‐conjugated backbone, the Lewis acidity of the metal ion, and the increase of ligand‐to‐metal ratio result in a substantial enhancement of β. The contribution of the metal‐to‐ligand (MLCT) transition to the molecular hyperpolarizability is also discussed with respect to octahedral d6 complexes (M=Fe, Ru).
Sintezekaet zo bet ur familh kemplezhioù metalek eizhpol, enno ligantoù daoubiridin arc'hwelekaet. O ferzhioù termek, optik linennek (euvriñ ha skingas) hag anlinennek zo bet termenet. Oberiegezh optikel anlinennek ar c'hediadoù‐se zo bet gallet termeniñ gant teknik skignañ harmonek ar sklêrijenn diouzh un hirder gwagennoù a 1.91 μm: talvoudegezhioù arβ0 zo etre 200 ha 657×10−30 ues evit ar c'hemplezhioù eizhtalek hag etre 70 ha 157×10−30 ues evit ar c'hemplezhioù pevarzalek. Gant ar c'hediad zink(II) 1 añ emañ an oberiegezh anlinennek eil‐urzh kreñvañ a vefe bet a‐viskoazh evit ur volekulenn eizhpol. Gant ar studiadenn‐mañ eo sklaer pegen levezonet eo ar perzhioù optik linennek hag anlinennek gant simetriezh ar molekul, anien al ligantoù (anien ar roer hag ar reizhiad treuzkas) hag anien ar c'hreiz metalek. Da skouer, gant hirder ar chadenn kediet, trenkted Lewis ar metal ha kresk ar c'heñver ligant/metal e kresk kalz ar β0. Mod‐all ez eus bet lakaet sklaer e ro an MLCT harp d'an oberiegezh optik anlinennek er c'hemplezhioù eizhtalek d6.
A series of D3 and D2d octupolar metal complexes, namely tris(bipyridyl)metal complexes (FeII, RuII, ZnII, HgII) and bis(bipyridyl)metal complexes (CuI, AgI, ZnII), featuring different functionalized bipyridyl ligands were prepared, an example of which is shown here. Their optical and nonlinear optical (NLO) properties are strongly influenced by the symmetry of the complexes, the nature of the ligands (donor endgroups and π linkers), and the nature of the metallic centers.</description><subject>2,2'-Dipyridyl - chemistry</subject><subject>absorption</subject><subject>coordination chemistry</subject><subject>fluorescence</subject><subject>ligand design</subject><subject>Metals, Heavy - chemistry</subject><subject>Molecular Structure</subject><subject>N ligands</subject><subject>nonlinear optics</subject><subject>Organometallic Compounds - chemical synthesis</subject><subject>Organometallic Compounds - chemistry</subject><issn>0947-6539</issn><issn>1521-3765</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2004</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNpFkVtLwzAYhoMobh5uvZRcebVqDk2aXuo2T0ynqOhdyNoUo-nBpEX7741uTgiEj_d5Al9eAA4wOsYIkZPsVZfHBKEYIYTJBhhiRnBEE842wRClcRJxRtMB2PH-LSApp3QbDDCjieCEDkH90Fftq_bGj-DMVFq5EVRVDu87lTvVmiy6rSv7G8B5E2Zl4Z2rG-1aoz2sCzjP2q6pbcgn9FedkByemaZ3Ju8tvNFtUMZ12Vj9pf0e2CqU9Xp_de-Cp_Pp4_gyms0vrsans8iQhJNIU6JIHC9owhjjfJGRcFKeUypIjBQqCloUDCOVsZTgeKEEFmFRJETMlcgw3QVHy3cbV3902reyND7T1qpK152XnIuUkUQE8HAFdotS57JxplSul39fFIB0CXwaq_v_HMmfAuRPAXJdgBxfTm_WU3CjpWt8q7_WrnLvkidhN_l8eyHTuxdCYobkNf0GWP6HLw</recordid><startdate>20040920</startdate><enddate>20040920</enddate><creator>Maury, Olivier</creator><creator>Viau, Lydie</creator><creator>Sénéchal, Katell</creator><creator>Corre, Brigitte</creator><creator>Guégan, Jean-Paul</creator><creator>Renouard, Thierry</creator><creator>Ledoux, Isabelle</creator><creator>Zyss, Joseph</creator><creator>Le Bozec, Hubert</creator><general>WILEY-VCH Verlag</general><general>WILEY‐VCH Verlag</general><scope>BSCLL</scope><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>7X8</scope></search><sort><creationdate>20040920</creationdate><title>Synthesis, Linear, and Quadratic-Nonlinear Optical Properties of Octupolar D3 and D2d Bipyridyl Metal Complexes</title><author>Maury, Olivier ; Viau, Lydie ; Sénéchal, Katell ; Corre, Brigitte ; Guégan, Jean-Paul ; Renouard, Thierry ; Ledoux, Isabelle ; Zyss, Joseph ; Le Bozec, Hubert</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-i2762-e32a244b3755566bc2bc296d338240a0ff3ff510ac59214ba81865308846a8c13</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2004</creationdate><topic>2,2'-Dipyridyl - chemistry</topic><topic>absorption</topic><topic>coordination chemistry</topic><topic>fluorescence</topic><topic>ligand design</topic><topic>Metals, Heavy - chemistry</topic><topic>Molecular Structure</topic><topic>N ligands</topic><topic>nonlinear optics</topic><topic>Organometallic Compounds - chemical synthesis</topic><topic>Organometallic Compounds - chemistry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Maury, Olivier</creatorcontrib><creatorcontrib>Viau, Lydie</creatorcontrib><creatorcontrib>Sénéchal, Katell</creatorcontrib><creatorcontrib>Corre, Brigitte</creatorcontrib><creatorcontrib>Guégan, Jean-Paul</creatorcontrib><creatorcontrib>Renouard, Thierry</creatorcontrib><creatorcontrib>Ledoux, Isabelle</creatorcontrib><creatorcontrib>Zyss, Joseph</creatorcontrib><creatorcontrib>Le Bozec, Hubert</creatorcontrib><collection>Istex</collection><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</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>Maury, Olivier</au><au>Viau, Lydie</au><au>Sénéchal, Katell</au><au>Corre, Brigitte</au><au>Guégan, Jean-Paul</au><au>Renouard, Thierry</au><au>Ledoux, Isabelle</au><au>Zyss, Joseph</au><au>Le Bozec, Hubert</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Synthesis, Linear, and Quadratic-Nonlinear Optical Properties of Octupolar D3 and D2d Bipyridyl Metal Complexes</atitle><jtitle>Chemistry : a European journal</jtitle><addtitle>Chemistry - A European Journal</addtitle><date>2004-09-20</date><risdate>2004</risdate><volume>10</volume><issue>18</issue><spage>4454</spage><epage>4466</epage><pages>4454-4466</pages><issn>0947-6539</issn><eissn>1521-3765</eissn><abstract>A series of D3 (FeII, RuII, ZnII, HgII) and D2d (CuI, AgI, ZnII) octupolar metal complexes featuring different functionalized bipyridyl ligands has been synthesized, and their thermal, linear (absorption and emission), and nonlinear optical (NLO) properties were determined. Their quadratic NLO susceptibilities were determined by harmonic light scattering at 1.91 μm, and the molecular hyperpolarizability (β0) values are in the range of 200–657×10−30 esu for octahedral complexes and 70–157×10−30 esu for tetrahedral complexes. The octahedral zinc(II) complex 1 e, which contains a 4,4′‐oligophenylenevinylene‐functionalized 2,2′‐bipyridine, exhibits the highest quadratic hyperpolarizability ever reported for an octupolar derivative (λmax=482 nm, β1.91(1 e)=870×10−30 esu, β0(1 e)=657×10−30 esu). Herein, we demonstrate that the optical and nonlinear optical (NLO) properties are strongly influenced by the symmetry of the complexes, the nature of the ligands (donor endgroups and π linkers), and the nature of the metallic centers. For example, the length of the π‐conjugated backbone, the Lewis acidity of the metal ion, and the increase of ligand‐to‐metal ratio result in a substantial enhancement of β. The contribution of the metal‐to‐ligand (MLCT) transition to the molecular hyperpolarizability is also discussed with respect to octahedral d6 complexes (M=Fe, Ru).
Sintezekaet zo bet ur familh kemplezhioù metalek eizhpol, enno ligantoù daoubiridin arc'hwelekaet. O ferzhioù termek, optik linennek (euvriñ ha skingas) hag anlinennek zo bet termenet. Oberiegezh optikel anlinennek ar c'hediadoù‐se zo bet gallet termeniñ gant teknik skignañ harmonek ar sklêrijenn diouzh un hirder gwagennoù a 1.91 μm: talvoudegezhioù arβ0 zo etre 200 ha 657×10−30 ues evit ar c'hemplezhioù eizhtalek hag etre 70 ha 157×10−30 ues evit ar c'hemplezhioù pevarzalek. Gant ar c'hediad zink(II) 1 añ emañ an oberiegezh anlinennek eil‐urzh kreñvañ a vefe bet a‐viskoazh evit ur volekulenn eizhpol. Gant ar studiadenn‐mañ eo sklaer pegen levezonet eo ar perzhioù optik linennek hag anlinennek gant simetriezh ar molekul, anien al ligantoù (anien ar roer hag ar reizhiad treuzkas) hag anien ar c'hreiz metalek. Da skouer, gant hirder ar chadenn kediet, trenkted Lewis ar metal ha kresk ar c'heñver ligant/metal e kresk kalz ar β0. Mod‐all ez eus bet lakaet sklaer e ro an MLCT harp d'an oberiegezh optik anlinennek er c'hemplezhioù eizhtalek d6.
A series of D3 and D2d octupolar metal complexes, namely tris(bipyridyl)metal complexes (FeII, RuII, ZnII, HgII) and bis(bipyridyl)metal complexes (CuI, AgI, ZnII), featuring different functionalized bipyridyl ligands were prepared, an example of which is shown here. Their optical and nonlinear optical (NLO) properties are strongly influenced by the symmetry of the complexes, the nature of the ligands (donor endgroups and π linkers), and the nature of the metallic centers.</abstract><cop>Weinheim</cop><pub>WILEY-VCH Verlag</pub><pmid>15378623</pmid><doi>10.1002/chem.200400012</doi><tpages>13</tpages></addata></record> |
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| subjects | 2,2'-Dipyridyl - chemistry absorption coordination chemistry fluorescence ligand design Metals, Heavy - chemistry Molecular Structure N ligands nonlinear optics Organometallic Compounds - chemical synthesis Organometallic Compounds - chemistry |
| title | Synthesis, Linear, and Quadratic-Nonlinear Optical Properties of Octupolar D3 and D2d Bipyridyl Metal Complexes |
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