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首页> 外文期刊>Chemistry: A European journal >Tris-cyclometalated iridium(III) complexes of carbazole(fluorenyl)pyridine ligands: Synthesis, redox and photophysical properties, and electrophosphoreseent light-emitting diodes
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Tris-cyclometalated iridium(III) complexes of carbazole(fluorenyl)pyridine ligands: Synthesis, redox and photophysical properties, and electrophosphoreseent light-emitting diodes

机译：咔唑（芴基）吡啶配体的三环金属化铱（III）配合物：合成，氧化还原和光物理性质以及电致磷光发光二极管

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摘要

Using ligands synthesized by Suzuki cross-coupling methodology, new phosphorescent homoleptic tris-cy-clometalated complexes have been obtained, namely fac-[Ir(Cz-2-Fl(n)Py)(3)] (1d-f) and fac-[Ir(Cz-3-Fl(n)Py)(3)] (2d-f), which are solution-processible triplet emitters (Cz denotes N-hexylcarbazole, n is the number of 9,9'-dihexylfluorene (Fl) units (n=0,1,2) and Py is pyridine). In all cases, Py and Fl are substituted at the 2- and 2,7-positions, respectively, and Cz moieties are substituted by either Py or Fl at the 2- or 3-positions, in series I and 2, respectively. The oxidation potential of 1d studied by cyclic voltammetry (E-1/2(ox) = 0.14 V versus Ag/AgNO3, CH2Cl2) is less positive (i.e. raised HOMO level) compared to that of the isomer 2d (E-1/2(ox) = 0.30 V), where the Cz-nitrogen is meta to the Ir center. Ligand-centered oxidations occur at more positive potentials, leading to 7+ oxidation states with good chemical reversibility and electrochemical quasi-reversibility, for example, for 2f E-pa(ox) =0.45 (1e), 0.95 (3e), 1.24V (3e). Striking differences are seen in the solution-state photophysical data between complexes [Ir(Cz-2-Py)(3)] (1d) and [Ir(Cz-3-Py)(3)] (2d), in which the Cz moiety is bonded directly to the metal center: for the latter there is an 85 nm blue-shift in emission, a decrease in the luminescence lifetime and an increase in the PLQY value. Organic light emitting devices were made by spin-coating using polyspirobifluorene:bis(triphenyl)diamine (PSBF:TAD) copolymer as host and the complexes Id or 2d as dopants. Turn-on voltages are low (3-4 V). With Id orange light is emitted at lambda(max) = 590 nm with an EQE of 1.3 % (at 7.5 mA cm(-2)) and an emission intensity (luminance) of 4354 cdm(-2) (at 267 mA m(-2)). The green emission from 2d devices 500 nm) is due to the reduced electron-donating ability of the carbazole unit in 2d. Recording the EL spectra of the Id device at 6 V (current density, 1.00 mA cm(-2)) established that the time to half brightness was about 9 h under continuous operation with no change in the spectral profile, confirming the high chemical stability of the complex.
机译：使用铃木交叉偶联方法合成的配体，已获得了新的磷光均三环氰基金属化配合物，即fac- [Ir（Cz-2-Fl（n）Py）（3）]（1d-f）和fac -[Ir（Cz-3-Fl（n）Py）（3）]（2d-f），它们是可溶液处理的三重态发射体（Cz表示N-己基咔唑，n是9,9'-二己基芴的数量（ F1）单元（n = 0,1,2），并且Py是吡啶）。在所有情况下，在系列I和2中，Py和F1分别在2-和2，7-位被取代，并且Cz部分分别在2-或3-位被Py或Fl取代。与异构体2d（E-1 / 2）相比，通过循环伏安法（E-1 / 2（ox）= 0.14 V对Ag / AgNO3，CH2Cl2）研究的1d的氧化电位正性较低（即，较高的HOMO水平）。 （ox）= 0.30 V），其中Cz-氮为Ir中心间位。以配体为中心的氧化在更高的正电势下发生，导致7+氧化态具有良好的化学可逆性和电化学准可逆性，例如，对于2f E-pa（ox）= 0.45（1e），0.95（3e），1.24V （3e）。在复合物[Ir（Cz-2-Py）（3）]（1d）和[Ir（Cz-3-Py）（3）]（2d）之间的溶液状态光物理数据中看到了惊人的差异。 Cz部分直接键合到金属中心：对于金属中心，发射中心发生85 nm蓝移，发光寿命减少，PLQY值增加。通过使用聚螺二芴：双（三苯基）二胺（PSBF：TAD）共聚物作为主体，配合物Id或2d作为掺杂剂通过旋涂法制造有机发光器件。开启电压低（3-4 V）。使用Id时，橙色光以λ（max）= 590 nm发射，EQE为1.3％（在7.5 mA cm（-2）时）和4354 cdm（-2）的发射强度（亮度）（在267 mA m（ -2））。来自2d器件500 nm的绿色发射是由于2d中咔唑单元的供电子能力降低。记录Id器件在6 V（电流密度，1.00 mA cm（-2））下的EL光谱，可以确定在连续操作下达到半亮度的时间约为9 h，光谱分布没有变化，从而确认了高化学稳定性的复杂。

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