{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,25]],"date-time":"2026-09-25T23:32:10Z","timestamp":1790379130020,"version":"4.1.0"},"reference-count":110,"publisher":"Wiley","issue":"27","license":[{"start":{"date-parts":[[2008,8,19]],"date-time":"2008-08-19T00:00:00Z","timestamp":1219104000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2008,9,19]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Three types of bithiophene\u2010fused benzo[<jats:italic>c<\/jats:italic>]phospholes were successfully prepared by Ti<jats:sup>II<\/jats:sup>\u2010mediated cyclization of the corresponding dialkynylated bithiophene derivatives as a key step. Each \u03c3<jats:sup>3<\/jats:sup>\u2010phosphorus center of the benzo[<jats:italic>c<\/jats:italic>]phosphole subunits was readily transformed into \u03c3<jats:sup>4<\/jats:sup>\u2010phosphorus center by Au coordination or oxygenation. In addition, the bithiophene subunit was functionalized at the \u03b1,\u03b1\u2032\u2010carbon atoms by Pd\u2010catalyzed cross\u2010coupling reactions with heteroarylmetals and by an S<jats:sub>N<\/jats:sub>Ar reaction with hexafluorobenzene. The experimentally observed results (NMR spectroscopy, X\u2010ray analysis, UV\/Vis absorption\/fluorescence spectroscopy, and cyclic\/differential\u2010pulse voltammetry) have revealed that the structural, optical, and electrochemical properties of the bithiophene\u2010fused benzo[<jats:italic>c<\/jats:italic>]phospholes vary considerably depending on the \u03c0\u2010conjugation modes at the bithiophene subunits and the substituents of the heterocyclopentadiene components. The appropriately ring\u2010annulated \u03c3<jats:sup>3<\/jats:sup>\u2010P derivatives and \u03c3<jats:sup>4<\/jats:sup>\u2010P\u2010AuCl complexes were found to emit fluorescence in the orange\u2013red region, and the \u03c3<jats:sup>4<\/jats:sup>\u2010P\u2010oxo derivatives proved to undergo reversible one\u2010electron reduction at \u22121.4 to \u22121.8\u2005V (vs ferrocene\/ferrocenium). These results indicate that the bithiophene\u2010fused benzo[<jats:italic>c<\/jats:italic>]phospholes possess narrow HOMO\u2013LUMO gaps and low\u2010lying LUMOs, which was confirmed by density functional theory calculations of their model compounds. The time\u2010of\u2010flight measurement of an ITO\/benzo[<jats:italic>c<\/jats:italic>]phosphole\/Al device showed that the electron mobility in the P\u2010oxo derivative is one\u2010order higher than that in Alq<jats:sub>3<\/jats:sub> at low electric fields. The present study demonstrates that the arene\u2010fused benzo[<jats:italic>c<\/jats:italic>]phosphole skeleton could be a highly promising platform for the construction of a new class of phosphole\u2010based optoelectrochemical materials.<\/jats:p>","DOI":"10.1002\/chem.200801017","type":"journal-article","created":{"date-parts":[[2008,8,19]],"date-time":"2008-08-19T08:57:16Z","timestamp":1219136236000},"page":"8102-8115","source":"Crossref","is-referenced-by-count":75,"title":["Comparative Study on the Structural, Optical, and Electrochemical Properties of Bithiophene\u2010Fused Benzo[<i>c<\/i>]phospholes"],"prefix":"10.1002","volume":"14","author":[{"given":"Yoshihiro","family":"Matano","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Tooru","family":"Miyajima","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Tatsuya","family":"Fukushima","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hironori","family":"Kaji","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yoshifumi","family":"Kimura","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hiroshi","family":"Imahori","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2008,9,15]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"For reviews see:"},{"key":"e_1_2_6_2_2","volume-title":"The Heterocyclic Chemistry of Phosphorus","author":"Quin L. D.","year":"1981"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr00084a005"},{"key":"e_1_2_6_4_2","volume-title":"Comprehensive Heterocyclic Chemistry, Vol.\u20052","author":"Quin L. D.","year":"1996"},{"key":"e_1_2_6_5_2","volume-title":"Phosphorus\u2013Carbon Heterocyclic Chemistry: The Rise of a New Domain","author":"Mathey F.","year":"2001"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr990321x"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200200557"},{"key":"e_1_2_6_7_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200200557"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.2174\/138527206775192997"},{"key":"e_1_2_6_9_2","unstructured":"For reviews see:"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0010-8545(03)00098-5"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr040179m"},{"key":"e_1_2_6_11_3","doi-asserted-by":"publisher","DOI":"10.1021\/cr068047b"},{"key":"e_1_2_6_12_2","first-page":"119","volume-title":"Functional Organic Materials","author":"Dyer P. 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Pat. 2003231741 2003;"},{"key":"e_1_2_6_43_2","doi-asserted-by":"publisher","DOI":"10.1246\/cl.2004.44"},{"key":"e_1_2_6_44_2","unstructured":"\u00a0"},{"key":"e_1_2_6_45_2","doi-asserted-by":"publisher","DOI":"10.1002\/masy.200390167"},{"key":"e_1_2_6_46_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200461301"},{"key":"e_1_2_6_46_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200461301"},{"key":"e_1_2_6_47_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200500152"},{"key":"e_1_2_6_48_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200700399"},{"key":"e_1_2_6_49_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jphotochem.2005.01.016"},{"key":"e_1_2_6_50_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol7030608"},{"key":"e_1_2_6_51_2","doi-asserted-by":"publisher","DOI":"10.1039\/b205663a"},{"key":"e_1_2_6_52_2","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.20591"},{"key":"e_1_2_6_53_2","unstructured":"\u00a0"},{"key":"e_1_2_6_54_2","doi-asserted-by":"publisher","DOI":"10.1039\/c29700000122"},{"key":"e_1_2_6_55_2","doi-asserted-by":"publisher","DOI":"10.1039\/p19730000927"},{"key":"e_1_2_6_56_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(01)87344-5"},{"key":"e_1_2_6_57_2","doi-asserted-by":"publisher","DOI":"10.1016\/0040-4020(75)80266-3"},{"key":"e_1_2_6_58_2","doi-asserted-by":"publisher","DOI":"10.1021\/om040022k"},{"key":"e_1_2_6_59_2","first-page":"809","volume-title":"Science of Synthesis, Vol.\u200510","author":"Aitken R. 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Prepr."},{"key":"e_1_2_6_64_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo0605748"},{"key":"e_1_2_6_65_2","doi-asserted-by":"publisher","DOI":"10.1002\/hlca.19960790318"},{"key":"e_1_2_6_66_2","unstructured":"\u00a0"},{"key":"e_1_2_6_67_2","doi-asserted-by":"publisher","DOI":"10.1016\/0040-4039(95)00727-T"},{"key":"e_1_2_6_68_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo961340z"},{"key":"e_1_2_6_69_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr990277l"},{"key":"e_1_2_6_70_2","first-page":"809","volume-title":"Science of Synthesis, Vol.\u20052","author":"Mikami K.","year":"2003"},{"key":"e_1_2_6_71_2","unstructured":"In single crystals of8\u2009aand9\u2009a one dichloromethane molecule was incorporated per two benzo[c]phosphole molecules whose structures are very similar. Therefore the data for one of the pair are listed for8\u2009aand9\u2009ain Table\u20051."},{"key":"e_1_2_6_72_2","unstructured":"\u00a0"},{"key":"e_1_2_6_73_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic00328a017"},{"key":"e_1_2_6_74_2","unstructured":"See refernce\u2005[4b]; Au\uf8ffP 2.2290(16)\u20132.2300(16)\u2005\u00c5; P\u2010Au\u2010Cl 171.64(7)\u2013174.63(8)\u00b0;"},{"key":"e_1_2_6_75_2","doi-asserted-by":"publisher","DOI":"10.1039\/B509277A"},{"key":"e_1_2_6_76_2","unstructured":"see reference\u2005[9c]; Au\uf8ffP 2.228(2)\u2005\u00c5; P\u2010Au\u2010Cl 175.59(7)\u00b0."},{"key":"e_1_2_6_77_2","unstructured":"The \u03c0\u2013\u03c0 distances between two planes in7\u2009a 8\u2009a and9\u2009aare about 3.4\u20133.6\u2005\u00c5."},{"key":"e_1_2_6_78_2","unstructured":"The electronic factor namely dipole\u2010dipole interaction of the adjacent chromophores may also assist the head\u2010to\u2010head orientation of7\u2009a 8\u2009a and9\u2009a."},{"key":"e_1_2_6_79_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.461824"},{"key":"e_1_2_6_80_2","unstructured":"The slower rise component was quenched by the addition of oxygen into the solution."},{"key":"e_1_2_6_81_2","unstructured":"In our preliminary communication we reported the optimized structures of P\u2010phenyl analogues of4\u2009m\u20136\u2009m whose HOMO and LUMO energies are as follows:4\u2009m\u2013Ph(\u22125.10\u2005eV and \u22121.89\u2005eV) 5\u2009m\u2013Ph(\u22125.16 and \u22121.96\u2005eV) 6\u2009m\u2013Ph(\u22125.55 and \u22121.60\u2005eV). See reference\u2005[15]."},{"key":"e_1_2_6_82_2","unstructured":"There are some reports on OLEDs using triorganylphosphine oxides as the component of electron transporting layers. For example see:"},{"key":"e_1_2_6_83_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.2193429"},{"key":"e_1_2_6_84_2","doi-asserted-by":"publisher","DOI":"10.1021\/cm0600677"},{"key":"e_1_2_6_85_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.1852707"},{"key":"e_1_2_6_86_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.2410236"},{"key":"e_1_2_6_87_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.2775323"},{"key":"e_1_2_6_88_2","first-page":"300","volume-title":"Optical Engineering Vol.\u200559","author":"Borsenberger P. M.","year":"1998"},{"key":"e_1_2_6_89_2","unstructured":"The electron mobilities of Alq3reported by Naka and co\u2010workers are about 2.5\u2005times larger than our experimental values. See:"},{"key":"e_1_2_6_90_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.125701"},{"key":"e_1_2_6_91_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0379-6779(99)00358-6"},{"key":"e_1_2_6_92_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol800684x"},{"key":"e_1_2_6_93_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4020(97)00427-4"},{"key":"e_1_2_6_94_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0021889894000221"},{"key":"e_1_2_6_95_2","unstructured":"DIRDIF99: Beurskens P.\u2005T. Admiraal G. Beurskens W.\u2005P. Bosman R. de\u2005Gelder R. Israel J.\u2005M.\u2005M. Smits The DIRDIF\u201099 program system Technical Report of the Crystallography Laboratory University of Nijmegen (The Netherlands) 1999."},{"key":"e_1_2_6_96_2","unstructured":"CrystalStructure 3.8.0: Crystal Structure Analysis Package Rigaku and Rigaku\/MSC (2000\u20132006). 9009 New Trails Dr. The Woodlands TX 77381 USA."},{"key":"e_1_2_6_97_2","unstructured":"G.\u2005M. Sheldrick SHELXL\u201097 University of G\u00f6ttingen (Germany) 1997."},{"key":"e_1_2_6_98_2","unstructured":"M.\u2005J. Frisch G.\u2005W. Trucks H.\u2005B. Schlegel G.\u2005E. Scuseria M.\u2005A. Robb J.\u2005R. Cheeseman J.\u2005A. Montgomery \u2005Jr. T. Vreven K.\u2005N. Kudin J.\u2005C. Burant J.\u2005M. Millam S.\u2005S. Iyengar J. Tomasi V. Barone B. Mennucci M. Cossi G. Scalmani N. Rega G.\u2005A. Petersson H. Nakatsuji M. Hada M. Ehara K. Toyota R. Fukuda J. Hasegawa M. Ishida T. Nakajima Y. Honda O. Kitao H. Nakai M. Klene X. Li J.\u2005E. Knox H.\u2005P. Hratchian J.\u2005B. Cross C. Adamo J. Jaramillo R. Gomperts R.\u2005E. Stratmann O. Yazyev A.\u2005J. Austin R. Cammi C. Pomelli J.\u2005W. Ochterski P.\u2005Y. Ayala K. Morokuma G.\u2005A. Voth P. Salvador J.\u2005J. Dannenberg V.\u2005G. Zakrzewski S. Dapprich A.\u2005D. Daniels M.\u2005C. Strain O. Farkas D.\u2005K. Malick A.\u2005D. Rabuck K. Raghavachari J.\u2005B. Foresman J.\u2005V. Ortiz Q. Cui A.\u2005G. Baboul S. Clifford J. Cioslowski B.\u2005B. Stefanov G. Liu A. Liashenko P. Piskorz I. Komaromi R.\u2005L. Martin D.\u2005J. Fox T. Keith M.\u2005A. Al\u2010Laham C.\u2005Y. Peng A. Nanayakkara M. Challacombe P.\u2005M.\u2005W. Gill B. Johnson W. Chen M.\u2005W. Wong C. Gonzalez J.\u2005A. 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