Mono and dinuclear iridium(<scp>iii</scp>) complexes featuring bis-tridentate coordination and Schiff-base bridging ligands: the beneficial effect of a second metal ion on luminescence

Puttock, Emma V.; Sil, Amit; Yufit, Dmitry S.; Williams, J. A. Gareth

doi:10.1039/d0dt01964j

Cited by 13 publications

(11 citation statements)

References 68 publications

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“…This reaction pattern is consistent with the literature precedents for formation of dichloride-bridged diiridium intermediate complexes. 41,42 Subsequently, they were heated in diethylene glycol monomethyl ether (DGME) solution for an extended period of time to afford the ultimate cyclometalating dimer complexes [Ir(κ 4 -Ln)(μ-Cl)] 2 (2a, n = 1; 2b, n = 2; 2c, n = 3). These two diiridium complexes were both confirmed by mass spectrometry and 1 H NMR and 19 F NMR spectra, respectively.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Stepwise Access of Emissive Ir(III) Complexes Bearing a Multi-Dentate Heteroaromatic Chelate: Fundamentals and Applications

Zheng

Zhu

et al. 2022

Inorg. Chem.

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Three multi-dentate coordinated chelates LnH2 (n = 1, 2, and 3), comprising a linked 1-(pyridin-2-yl)ethylbenzene and one pyrazolyl pyridine unit and showing either tridentate or tetradentate coordination modes, are successfully designed and synthesized. Dinuclear Ir(III) complexes [Ir(κ4-Ln)(μ-Cl)]2 bearing tetradentate coordinated κ4-Ln chelate (2a, n = 1; 2b, n = 2; 2c, n = 3) were next obtained en route from the respective intermediate [Ir(κ3-LnH)Cl(μ-Cl)]2 bearing the tridentate coordinated κ3-LnH chelate (1a, n = 1; 1b, n = 2; 1c, n = 3). Next, mononuclear Ir(III) complexes Ir(κ 4-Ln)(thd) (3a, n = 1; 3b, n = 2; 3c, n = 3) with the tetradentate chelate were obtained upon treatment of 2 with 2,2,6,6-tetramethyl-3,5-heptanedione (thd)H in the presence of K2CO3. Concurrently, methylation of 2c in the presence of MeI and n Bu4NCl afforded tridentate Ir(κ3-L3HMe)Cl3 (4) and, next, can be converted to tetradentate Ir(κ 4-L3Me)Cl2 (5) by further cyclometalation and HCl elimination in refluxing diethylene glycol monoethyl ether solution. The Ir(III) complexes 3a, 4, and 5 were unambiguously identified using spectroscopic methods, together with single-crystal X-ray structural analyses on Ir(III) derivatives 3a, 4, and 5. Their photophysical and ,electrochemical properties and device fabrication properties were also investigated and compared with results from theoretical studies.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Stepwise Access of Emissive Ir(III) Complexes Bearing a Multi-Dentate Heteroaromatic Chelate: Fundamentals and Applications

Zheng

Zhu

et al. 2022

Inorg. Chem.

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“…The outstanding device performance of these dinuclear Pt(II) complexes can be partly attributed to the stronger spin–orbit coupling effect induced by the second metal center, which increases the luminous efficiency of related complexes. ,, For example, the PLQYs of PyDPt and QuDPt in doped films were as high as 0.79 and 0.71, respectively. In addition, at a low concentration of 1 wt %, the doped films showed uniform and smooth surfaces with small root-mean-square roughness values of 0.41, 0.52, and 0.42 nm for films doped with PyDPt , ThDPt , and QuDPt , respectively (Figure S6).…”

Section: Resultsmentioning

confidence: 99%

Developing Efficient Dinuclear Pt(II) Complexes Based on the Triphenylamine Core for High-Efficiency Solution-Processed OLEDs

Sun

Liu

Guo

et al. 2021

ACS Appl. Mater. Interfaces

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The various applications of dinuclear complexes have attracted increasing attention. However, the electroluminescence efficiencies of dinuclear Pt(II) complexes are far from satisfactory. Herein, based on the triphenylamine core, we develop four dinuclear Pt(II) complexes that cover the emission colors from yellow to red with high photoluminescence quantum efficiencies of up to 0.79 in doped films. The solid-state structure of PyDPt is revealed by the single-crystal X-ray diffraction investigation. Besides, solution-processed OLEDs have been fabricated with different electron transport materials. With higher electron mobility and excellent hole-blocking ability, 1,3,5-tri(m-pyridin-3-ylphenyl)benzene (TmPyPB) can help to realize good charge balance in related OLEDs. In addition, angle-dependent PL spectra reveal the preferentially horizontal orientation of these dinuclear Pt(II) complexes in doped CBP films, which benefits the outcoupling efficiencies. Therefore, the yellow OLED based on PyDPt shows unexpected high performance with a peak current efficiency of up to 78.7 cd/A and an external quantum efficiency of up to 22.4%, which is the highest EQE reported for OLEDs based on dinuclear Pt(II) complexes so far. This study demonstrates the great potential of developing dinuclear Pt(II) complexes for achieving excellent electroluminescence efficiencies.

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“…B. in mehrkernigen Komplexen. [168] Eine weitere Strategie, die für CT-Emitter gründlich erforscht wurde, ist die thermisch aktivierte verzögerte Fluoreszenz (TADF, Abbildung 7). [84,109,[169][170][171][172][173] Dabei befindet sich ein emittierender Triplett-Zustand über ISC und Rück-ISC im thermischen Gleichgewicht mit einem energetisch höher liegenden Singulett-Zustand (ΔE ST < 1600 cm À 1 ).…”

Section: Beeinflussung Der Emissionslebensdauerunclassified

Charge‐Transfer und Spin‐Flip‐Zustände als sich ergänzende Gegensätze

Kitzmann

Heinze

2023

Angewandte Chemie

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Übergangsmetallkomplexe mit photoaktiven Charge‐Transfer‐Zuständen sind in der Literatur allgegenwärtig. Insbesondere [Ru(bpy)3]2+ (bpy=2,2′‐Bipyridin) mit seiner Metall‐zu‐Ligand‐Charge‐Transfer‐Emission hat sich als Schlüsselkomplex etabliert. Indes ist auch das Interesse an metallzentrierten Spin‐Flip‐Zuständen gestiegen, nachdem der molekulare Rubin [Cr(ddpd)2]3+ (ddpd=N,N′‐Dimethyl‐N,N′‐dipyridin‐2‐yl‐pyridin‐2,6‐diamin) Designprinzipien für intensive Emission von photostabilen Chrom(III)‐Komplexen enthüllt hat. In diesem Aufsatz werden die Eigenschaften von emissiven Charge‐Transfer‐ und Spin‐Flip‐Zuständen anhand der Prototypen [Ru(bpy)3]2+ bzw. [Cr(ddpd)2]3+ verglichen. Wir erörtern die angeregten Zustände, die Anpassbarkeit ihrer Energie und Lebensdauer sowie ihre Reaktion auf externe Stimuli. Schließlich werden die Stärken und Schwächen von Charge‐Transfer‐ und Spin‐Flip‐Zuständen in Anwendungen wie Photokatalyse und zirkular polarisierter Lumineszenz aufgezeigt.

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Mono and dinuclear iridium(iii) complexes featuring bis-tridentate coordination and Schiff-base bridging ligands: the beneficial effect of a second metal ion on luminescence

Abstract: Ditopic bis-N^N^O-coordinating ligands, prepared by Schiff base chemistry, lead to dinuclear iridium complexes that emit much more brightly than their mononuclear counterparts.

Cited by 13 publications

References 68 publications

Stepwise Access of Emissive Ir(III) Complexes Bearing a Multi-Dentate Heteroaromatic Chelate: Fundamentals and Applications

Stepwise Access of Emissive Ir(III) Complexes Bearing a Multi-Dentate Heteroaromatic Chelate: Fundamentals and Applications

Developing Efficient Dinuclear Pt(II) Complexes Based on the Triphenylamine Core for High-Efficiency Solution-Processed OLEDs

Charge‐Transfer und Spin‐Flip‐Zustände als sich ergänzende Gegensätze

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