{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,29]],"date-time":"2026-09-29T01:01:36Z","timestamp":1790643696514,"version":"4.1.0"},"reference-count":78,"publisher":"Wiley","issue":"3","license":[{"start":{"date-parts":[[2007,11,21]],"date-time":"2007-11-21T00:00:00Z","timestamp":1195603200000},"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":[[2008,1,18]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>We report the synthesis, characterisation, photophysical and electrochemical properties of a series of cationic cyclometallated Ir<jats:sup>III<\/jats:sup> complexes of general formula [Ir(ppy)<jats:sub>2<\/jats:sub>(phen)]PF<jats:sub>6<\/jats:sub> (ppy=2\u2010phenylpyridine, phen=a substituted phenanthroline). A feature of these complexes is that the phen ligands are substituted with one or two 9,9\u2010dihexylfluorenyl substituents to provide extended \u03c0 conjugation, for example, the 3\u2010[2\u2010(9,9\u2010dihexylfluorenyl)]phenanthroline and 3,8\u2010bis[2\u2010(9,9\u2010dihexylfluorenyl)]phenanthroline ligands afford complexes <jats:bold>6<\/jats:bold> and <jats:bold>9<\/jats:bold>, respectively. A single\u2010crystal X\u2010ray diffraction study of a related complex <jats:bold>18<\/jats:bold> containing the 3,8\u2010bis(4\u2010iodophenyl)phenanthroline ligand, revealed an octahedral coordination of the Ir atom, in which the metallated C atoms of the ppy ligands occupy <jats:italic>cis<\/jats:italic> positions. The complexes <jats:bold>6<\/jats:bold> and <jats:bold>9<\/jats:bold> displayed reversible oxidation waves in cyclic voltammetric studies (<jats:styled-content>${E{{{\\rm ox}\\hfill \\atop 1\/2\\hfill}}}$<jats:inline-graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" xlink:href=\"graphic\/tex2gif-ueqn-1.gif\" xlink:title=\"equation image\"\/><\/jats:styled-content>=+1.18 and +1.20\u2005V, respectively, versus Ag\/Ag<jats:sup>+<\/jats:sup> in CH<jats:sub>2<\/jats:sub>Cl<jats:sub>2<\/jats:sub>) assigned to the metal\u2010centred Ir<jats:sup>III<\/jats:sup>\/Ir<jats:sup>IV<\/jats:sup> couple. The complexes exhibit strong absorption in the UV region in solution spectra, due to spin\u2010allowed ligand\u2010centred (LC) <jats:sup>1<\/jats:sup>\u03c0\u2013\u03c0* transitions; moderately intense bands occur at approximately 360\u2013390\u2005nm which are red\u2010shifted with increased ligand length. The photoluminescence spectra of all the complexes were characterised by a broad band at <jats:italic>\u03bb<\/jats:italic><jats:sub>max<\/jats:sub>\u2248595\u2005nm assigned to a combination of <jats:sup>3<\/jats:sup>MLCT and <jats:sup>3<\/jats:sup>\u03c0\u2192\u03c0* states. The long emission lifetimes (in the microsecond time\u2010scale) are indicative of phosphorescence: the increased ligand conjugation length in complexes <jats:bold>9<\/jats:bold> and <jats:bold>17<\/jats:bold> leads to increased lifetimes for the complexes (<jats:italic>\u03c4<\/jats:italic>=2.56 and 2.57\u2005\u03bcs in MeCN, respectively) compared to monofluorenyl analogues <jats:bold>6<\/jats:bold> and <jats:bold>15<\/jats:bold> (<jats:italic>\u03c4<\/jats:italic>=1.43 and 1.39\u2005\u03bcs, respectively). DFT calculations of the geometries and electronic structures of complexes <jats:bold>6<\/jats:bold>\u2032, <jats:bold>9<\/jats:bold>\u2032 (for both singlet ground state (S<jats:sub>0<\/jats:sub>) and triplet first excited (T<jats:sub>1<\/jats:sub>) states) and <jats:bold>18<\/jats:bold> have been performed. In the singlet ground state (S<jats:sub>0<\/jats:sub>) HOMO orbitals in the complexes are spread between the Ir atom and benzene rings of the phenylpyridine ligand, whereas the LUMO is mainly located on the phenanthroline ligand. Analysis of orbital localisations for the first excited (T<jats:sub>1<\/jats:sub>) state have been performed and compared with spectroscopic data. Spin\u2010coated light\u2010emitting cells (LECs) have been fabricated with the device structures ITO\/PEDOT:PSS\/Ir complex\/Al, or Ba capped with Al (ITO=indium tin oxide, PEDOT=poly(3,4\u2010ethylenedioxythiophene), PSS=poly(styrene) sulfonate). A maximum brightness efficiency of 9\u2005cd\u2009A<jats:sup>\u22121<\/jats:sup> has been attained at a bias of 9\u2005V for <jats:bold>17<\/jats:bold> with a Ba\/Al cathode. The devices operated in air with no reduction in efficiency after storage for one week in air.<\/jats:p>","DOI":"10.1002\/chem.200700308","type":"journal-article","created":{"date-parts":[[2007,11,21]],"date-time":"2007-11-21T12:17:31Z","timestamp":1195647451000},"page":"933-943","source":"Crossref","is-referenced-by-count":106,"title":["Cationic Bis\u2010cyclometallated Iridium(<scp>III)<\/scp> Phenanthroline Complexes with Pendant Fluorenyl Substituents: Synthesis, Redox, Photophysical Properties and Light\u2010Emitting Cells"],"prefix":"10.1002","volume":"14","author":[{"given":"Xianshun","family":"Zeng","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Mustafa","family":"Tavasli","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Igor\u2005F.","family":"Perepichka","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Andrei\u2005S.","family":"Batsanov","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Martin\u2005R.","family":"Bryce","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Chien\u2010Jung","family":"Chiang","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Carsten","family":"Rothe","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Andrew\u2005P.","family":"Monkman","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2008,1,10]]},"reference":[{"key":"e_1_2_5_1_2","unstructured":"\u00a0"},{"key":"e_1_2_5_2_2","doi-asserted-by":"publisher","DOI":"10.1039\/B304265K"},{"key":"e_1_2_5_3_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.200300249"},{"key":"e_1_2_5_4_2","doi-asserted-by":"publisher","DOI":"10.1039\/b103490c"},{"key":"e_1_2_5_5_2","unstructured":"\u00a0"},{"key":"e_1_2_5_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic0008969"},{"key":"e_1_2_5_7_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.1355007"},{"key":"e_1_2_5_8_2","doi-asserted-by":"publisher","DOI":"10.1246\/cl.2005.1378"},{"key":"e_1_2_5_9_2","doi-asserted-by":"publisher","DOI":"10.1039\/B406851C"},{"key":"e_1_2_5_10_2","unstructured":"\u00a0"},{"key":"e_1_2_5_11_2","doi-asserted-by":"publisher","DOI":"10.1039\/b207502d"},{"key":"e_1_2_5_12_2","doi-asserted-by":"publisher","DOI":"10.1039\/b313843g"},{"key":"e_1_2_5_13_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.200400114"},{"key":"e_1_2_5_14_2","doi-asserted-by":"publisher","DOI":"10.1039\/b515549e"},{"key":"e_1_2_5_15_2","doi-asserted-by":"publisher","DOI":"10.1002\/adfm.200600099"},{"key":"e_1_2_5_16_2","unstructured":"\u00a0"},{"key":"e_1_2_5_17_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja021413y"},{"key":"e_1_2_5_18_2","doi-asserted-by":"publisher","DOI":"10.1021\/cm049701b"},{"key":"e_1_2_5_19_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic048599h"},{"key":"e_1_2_5_20_2","unstructured":"\u00a0"},{"key":"e_1_2_5_21_2","doi-asserted-by":"publisher","DOI":"10.1038\/35001541"},{"key":"e_1_2_5_22_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja003693s"},{"key":"e_1_2_5_23_2","doi-asserted-by":"publisher","DOI":"10.1021\/cm030410x"},{"key":"e_1_2_5_24_2","doi-asserted-by":"publisher","DOI":"10.1002\/adma.200400284"},{"key":"e_1_2_5_25_2","volume-title":"Organic Electroluminescence","year":"2005"},{"key":"e_1_2_5_26_2","first-page":"413","volume-title":"Organic Light\u2010Emitting Materials and Devices","author":"Perepichka D. 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