Synthesis and characterization of phosphorescent cyclometalated iridium complexes
Synthesis and characterization of phosphorescent cyclometalated iridium complexes
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DOI：
10.1021/ic0008969
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发表时间：
2001-03-26
影响因子：
4.6
通讯作者：
Thompson, ME
中科院分区：
文献类型：
--
作者：
Lamansky, S;Djurovich, P;Thompson, ME
报道了不同环化配体与八面体金属铱配合物的制备、晶体物理和固态结构。氯化镧。nH（2）O干净地环化许多不同的化合物（即，2-苯基吡啶，2-（对甲苯基）吡啶，苯并喹啉，2-苯基苯并噻唑，2-（1-萘基）苯并噻唑和2-苯基喹啉），以良好的产率形成相应的氯桥二聚体，C布尔ANDN（2）Ir（μ-Cl）（2）IrC布尔ANDN（2）（C布尔AND N是环化配体）。这些氯桥二聚体与乙酰丙酮（acacH）和其他双齿单阴离子配体如吡啶甲酸（picH）和N-甲基水杨酰亚胺（salH）反应，得到单体C布尔ANDN（2）Ir（LX）配合物（LX = acac，pie，sal）。这些配合物的发射光谱在很大程度上取决于环化配体的性质，导致这里报道的配合物的λ（max）值从510至606 nm。铱的强自旋-轨道耦合将形式上禁止的（MLCT）-M-3和3 π-π * 跃迁与允许的（MLCT）-M-1混合，导致具有良好量子效率（0.1-0.4）和微秒范围内的室温寿命的强磷光。C布尔ANDN（2）Ir（LX）配合物的发射光谱与相同配体的fac-IrC布尔ANDN（3）配合物的发射光谱惊人地相似，尽管这两种配合物的结构明显不同。两个C布尔ANDN（2）Ir（acac）配合物的晶体结构（即，C boolean ANDN = ppy和tpy）。两个配合物显示两个环化配体的顺式-C，C '，反式-N，N'配置，类似于具有“C布尔ANDN（2）Ir”片段的其他配合物的结构。NMR数据（H-1和C-13）支持所有C布尔ANDN（2）Ir（LX）配合物的类似结构。（ppy）（2）Ir（acac）和（tpy）（2）Ir（acac）的分子间紧密接触导致ppy和tpy配合物晶体样品的发射光谱相对于其溶液光谱显著红移。
The preparation, photophysics, and solid state structures of octahedral organometallic Ir complexes with several different cyclometalated ligands are reported. LrCl3 . nH(2)O cleanly cyclometalates a number of different compounds (i.e., 2-phenylpyridine, 2-(p-tolyl)pyridine, benzoquinoline, 2-phenylbenzothiazole, 2-(1-naphthyl)benzothiazole, and 2-phenylquinoline), forming the corresponding chloride-bridged dimers, C boolean ANDN(2)Ir(mu -Cl)(2)IrC boolean ANDN(2) (C boolean AND Nis a cyclometalated ligand) in good yield. These chloride-bridged dimers react with acetyl acetone (acacH) and other bidentate, monoanionic ligands such as picolinic acid (picH) and N-methylsalicylimine (salH)\ to give monomeric C boolean ANDN(2)Ir(LX) complexes (LX = acac, pie, sal). The emission spectra of these complexes are largely governed by the nature of the cyclometalating ligand, leading to lambda (max) values from 510 to 606 nm for the complexes reported here. The strong spin-orbit coupling of iridium mixes the formally forbidden (MLCT)-M-3 and 3 pi-pi* transitions with the allowed (MLCT)-M-1, leading to a strong phosphorescence with good quantum efficiencies (0.1-0.4) and room temperature lifetimes in the microsecond regime. The emission spectra of the C boolean ANDN(2)Ir(LX) complexes are surprisingly similar to the fac-IrC boolean ANDN(3) complex of the same ligand, even though the structures of the two complexes are markedly different. The crystal structures of two of the C boolean ANDN(2)Ir(acac) complexes (i.e., C boolean ANDN = ppy and tpy) have been determined. Both complexes show cis-C,C', trans-N,N' disposition of the two cyclometalated ligands, similar to the structures reported for other complexes with a "C boolean ANDN(2)Ir" fragment. NMR data (H-1 and C-13) support a similar structure for all of the C boolean ANDN(2)Ir(LX) complexes. Close intermolecular contacts in both (ppy)(2)Ir(acac) and (tpy)(2)Ir(acac) lead to significantly red shifted emission spectra for crystalline samples of the ppy and tpy complexes relative to their solution spectra.