Xu Ke, Chen Bu-Lin, Zhang Rui, Liu Li, Zhong Xin-Xin, Wang Lei, Li Feng-Yan, Li Guang-Hua, Alamry Khalid A, Li Fa-Bao, Wong Wai-Yeung, Qin Hai-Mei
Hubei Collaborative Innovation Center for Advanced Organic Chemical Materials, Ministry of Education Key Laboratory for the Synthesis and Application of Organic Functional Molecules, School of Chemistry and Chemical Engineering, Hubei University, Wuhan 430062, P. R. China.
Dalton Trans. 2020 May 14;49(18):5859-5868. doi: 10.1039/c9dt04701h. Epub 2020 Apr 20.
Highly emissive copper(i) halide nanoclusters showing thermally activated delayed fluorescence (TADF) have been paid much attention, but rarely reported so far. Herein, a hexanuclear copper(i) iodide cluster containing a tridentate N∧P∧N ligand, [CuI(ppda)] {ppda = 2-[2-(dimethylamino)phenyl(phenyl)phosphino]-N,N-dimethylaniline}, was synthesized. All six copper atoms are four-coordinate, including four CuPNI and two CuI units. This complex exhibits intense white emission in the powder state at room temperature and shows a peak at a wavelength of 535 nm (Φ = 0.36) with a microsecond lifetime (τ = 4.4 μs). Emission colors can be largely tuned from blue to white to yellow, from the crystal to powder to film state at 297 K. The emission of [CuI(ppda)] originates from a combination of MLCT and XLCT transitions. This complex showed good thermal stability. A solution-processed, nondoped device of complex [CuI(ppda)] exhibits stable yellow emission with the CIE coordinates (x, y) of (0.43, 0.51). [CuI(ppda)] also shows reasonable photocatalytic H evolution activity under visible-light irradiation.
具有热激活延迟荧光（TADF）的高发射性卤化亚铜（I）纳米团簇已备受关注，但迄今为止报道较少。在此，合成了一种含有三齿N∧P∧N配体的六核碘化亚铜簇[CuI(ppda)] {ppda = 2-[2-(二甲基氨基)苯基(苯基)膦基]-N,N-二甲基苯胺}。所有六个铜原子均为四配位，包括四个CuPNI和两个CuI单元。该配合物在室温下的粉末状态下表现出强烈的白色发射，在波长535 nm处有一个峰值（Φ = 0.36），寿命为微秒级（τ = 4.4 μs）。在297 K下，从晶体到粉末再到薄膜状态，发射颜色可从蓝色大幅调至白色再到黄色。[CuI(ppda)]的发射源于MLCT和XLCT跃迁的组合。该配合物表现出良好的热稳定性。基于配合物[CuI(ppda)]的溶液处理非掺杂器件表现出稳定的黄色发射，CIE坐标（x, y）为（0.43, 0.51）。[CuI(ppda)]在可见光照射下也表现出合理的光催化析氢活性。
