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Preparation of Phosphorescent Iridium(III) Complexes with a Dianionic C,C,C,C-Tetradentate Ligand
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2018-03-14 00:00:00 , DOI: 10.1021/acs.inorgchem.7b02993
Miguel A. Esteruelas 1 , Ana M. López 1 , Enrique Oñate 1 , Ainhoa San-Torcuato 1 , Jui-Yi Tsai 2 , Chuanjun Xia 2
Affiliation  

The preparation and photophysical properties of heteroleptic iridium(III) complexes containing a dianionic C,C,C,C-tetradentate ligand and a cyclometalated phenylpyridine group are described. Complex [Ir(μ-OMe)(COD)]2 (1, COD = 1,5-cyclooctadiene) reacts with 1,1-diphenyl-3,3-butylenediimidazolium iodide ([PhIm(CH2)4ImPh]I2), in the presence NaOtBu, to give [Ir(μ-I){κ4-C,C,C,C-[C6H4Im(CH2)4ImC6H4]}]2 (2), which leads to {[Ir{κ4-C,C,C,C-[C6H4Im(CH2)4ImC6H4]}]2(μ-OH)(μ-OMe)} (3) by treatment first with silver trifluoromethanesulfonate (AgOTf) in acetone–dichloromethane and subsequently with KOH in methanol. The reaction of 2 with AgOTf and acetonitrile affords the bis(solvento) complex [Ir{κ4-C,C,C,C-[C6H4Im(CH2)4ImC6H4]}(CH3CN)2]OTf (4). The latter promotes the pyridyl-supported heterolytic ortho-CH bond activation of the phenyl group of 2-phenylpyridine, 2-(2,4-difluorophenyl)pyridine, 2-(p-tolyl)pyridine, and 5-methyl-2-phenylpyridine to yield Ir{κ4-C,C,C,C-[C6H4Im(CH2)4ImC6H4]}{κ2-C,N-[Ar-py]} (Ar-py = C6H4-py (5), C6H2F2-py (6), C6H3Me-py (7), C6H4-Mepy (8)) using (piperidinomethyl)polystyrene as an external base. Complexes 58 are blue-green emitters, which display short lifetimes (0.6–4.8 μs) and quantum yields close to unity in both doped poly(methyl methacrylate) films at 5 wt % and in 2-methyltetrahydrofuran at room temperature.

中文翻译:

带有C,C,C,C-四齿配体的双阳离子磷光铱(III)配合物的制备

描述了含双阴离子C,C,C,C-四齿配体和环金属化苯基吡啶基团的杂铱铱(III)配合物的制备和光物理性质。络合物[Ir(μ-OMe)(COD)] 21,COD = 1,5-环辛二烯)与1,1-二苯基-3,3-丁二咪唑碘化物([PhIm(CH 24 ImPh] I 2),在存在的NaO卜,得到的[Ir(μ-I){κ 4 - çççç - [C 6 H ^ 4 IM(CH 24 IMC 6 ħ 4 ]}]22),这导致{物[Ir {κ 4 - ÇÇÇÇ - [C 6 H ^ 4 IM(CH 24 IMC 6 ħ 4 ]}] 2(μ-OH)(μ- OMe)}(3),首先在丙酮-二氯甲烷中用三氟甲磺酸银(AgOTf)处理,然后在甲醇中用KOH处理。的反应2用的AgOTf和乙腈,得到双(solvento)配合物[Ir {κ 4 - ÇÇÇÇ - [C6 H 4 Im(CH 24 ImC 6 H 4 ]}(CH 3 CN)2 ] OTf(4)。后者促进2-苯基吡啶,2-(2,4-二氟苯基)吡啶,2-(甲苯基)吡啶和5-甲基-2-苯基吡啶的苯基的吡啶基支撑的杂位邻位-CH键活化。得到的Ir {κ 4 - çççç - [C 6 H ^ 4 IM(CH 24 IMC 6 ħ 4 ]} {κ2 - CN- [Ar-py]}(Ar-py = C 6 H 4 -py(5),C 6 H 2 F 2 -py(6),C 6 H 3 Me-py(7),使用(哌啶子基甲基)聚苯乙烯作为外部碱的C 6 H 4 -Mepy(8))。络合物5 - 8是蓝绿色发射器,其靠近在两个掺杂的聚(甲基丙烯酸甲酯)在统一5重量%的薄膜和在室温下的2-甲基四氢呋喃显示短的寿命(0.6-4.8微秒)和量子产率。
更新日期:2018-03-14
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