Facendola John W, Seifrid Martin, Siegel Jay, Djurovich Peter I, Thompson Mark E
Department of Chemistry, University of Southern California, Los Angeles, California 90089, USA.
Dalton Trans. 2015 May 14;44(18):8456-66. doi: 10.1039/c4dt03541k.
Synthesis, structural and characterization data are provided for Pt(II) and Ir(III) complexes cyclometalated with 2-(corannulene)pyridine (corpy), (corpy)Pt(dpm) and (corpy)Ir(ppz)2 (dpm = dipivaloylmethanato, ppz = 1-phenylpyrazolyl). A third compound, (phenpy)Ir(ppz)2 (phenpy = 2-(5-phenanthryl)pyridyl), was also prepared to mimic the steric bulk of (corpy)Ir(ppz)2. X-ray analysis reveals bowl depths of 0.895 Å for (corpy)Pt(dpm) and 0.837 Å in (corpy)Ir(ppz)2. Neither complex displayed bowl-to-bowl stacking in the crystal lattice. A fluxional process for (corpy)Ir(ppz)2 attributed to bowl inversion of corrannulene is observed in solution with a barrier (ΔG(‡) = 13 kcal mol(-1)) and rate (k = 2.5 × 10(3) s(-1)) as determined using variable temperature (1)H NMR spectroscopy. All of the complexes display red phosphorescence at room temperature with quantum yields of 0.05 in solution and 0.2 in polymethyl methacrylate (PMMA).
提供了用2-(碗烯)吡啶（corpy）、(corpy)Pt(dpm)和(corpy)Ir(ppz)₂（dpm = 二(新戊酰基)甲烷，ppz = 1-苯基吡唑基）环金属化的Pt(II)和Ir(III)配合物的合成、结构和表征数据。还制备了第三种化合物(phenpy)Ir(ppz)₂（phenpy = 2-(5-菲基)吡啶基）以模拟(corpy)Ir(ppz)₂的空间体积。X射线分析显示，(corpy)Pt(dpm)的碗深为0.895 Å，(corpy)Ir(ppz)₂的碗深为0.837 Å。两种配合物在晶格中均未显示碗对碗堆积。在溶液中观察到(corpy)Ir(ppz)₂的一种归因于碗烯碗翻转的动态过程，其势垒（ΔG(‡) = 13 kcal mol⁻¹）和速率（k = 2.5 × 10³ s⁻¹）通过变温¹H NMR光谱测定。所有配合物在室温下均呈现红色磷光，在溶液中的量子产率为0.05，在聚甲基丙烯酸甲酯（PMMA）中的量子产率为0.2。
