کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
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1325648 | 977394 | 2010 | 9 صفحه PDF | دانلود رایگان |
![عکس صفحه اول مقاله: Neutral and cationic cyclometallated Ir(III) complexes of anthra[1,2-d]imidazole-6,11-dione-derived ligands: Syntheses, structures and spectroscopic characterisation Neutral and cationic cyclometallated Ir(III) complexes of anthra[1,2-d]imidazole-6,11-dione-derived ligands: Syntheses, structures and spectroscopic characterisation](/preview/png/1325648.png)
The syntheses of two new ligands and five new heteroleptic cyclometallated Ir(III) complexes are reported. The ligands are based upon a functionalised anthra[1,2-d]imidazole-6,11-dione core giving LH1−3 incorporating a pendant pyridine, quinoline or thiophene unit respectively. Neutrally charged, octahedral complexes [Ir(ppy)2(L1−3)] are chelated by two cyclometallated phenylpyridine (ppy) ligands and a third, ancillary deprotonated ligand L1−3, whilst cationic analogues could only be isolated for [Ir(ppy)2(LH1−2)][PF6]. X-ray crystal structures for [Ir(ppy)2(L1)], [Ir(ppy)2(LH1)][PF6] and [Ir(ppy)2(L2)] showed the complexes adopt a distorted octahedral coordination geometry, with the anthra[1,2-d]imidazole-6,11-dione ligands coordinating in a bidentate fashion. Preliminary DFT calculations revealed that for the complexes of LH1 and LH2 the LUMO is exclusively localized on the ancillary ligand, whereas the nature of the HOMO depends on the protonation state of the ancillary ligand, often being composed of both Ir(III) and phenylpyridine character. UV–vis. and luminescence data showed that the ligands absorb into the visible region ca. 400 nm and emit ca. 560 nm, both of which are attributed to an intra-ligand CT transition within the anthra[1,2-d]imidazole-6,11-dione core. The complexes display absorption bands attributed to overlapping ligand-centred and 1MLCT-type electronic transitions, whilst only [Ir(ppy)2(L2)] appeared to possess typical 3MLCT behaviour (λem = 616 nm; τ = 96 ns in aerated MeCN). The remaining complexes were generally visibly emissive (λem ≈ 560–570 nm; τ < 10 ns in aerated MeCN) with very oxygen-sensitive lifetimes more indicative of ligand-centred processes.
Aromatic aldehydes can be condensed with 1,2-diaminoanthaquinone to yield a series of donor appended anthra[1,2d]imidazole-6,11-dione ligands which can be coordinated to Ir(III) giving either cationic or neutral complexes. Generally, the resultant complexes are emissive with either ligand-centred fluorescence or long-lived 3MLCT emission depending on the nature of the complex.Figure optionsDownload as PowerPoint slide
Journal: Journal of Organometallic Chemistry - Volume 695, Issue 22, 15 October 2010, Pages 2401–2409