Romanov Alexander S, Jones Saul T E, Gu Qinying, Conaghan Patrick J, Drummond Bluebell H, Feng Jiale, Chotard Florian, Buizza Leonardo, Foley Morgan, Linnolahti Mikko, Credgington Dan, Bochmann Manfred
School of Chemistry , University of East Anglia , Norwich Research Park , Norwich , NR4 7TJ , UK . Email:
Department of Physics , Cavendish Laboratory , Cambridge University , Cambridge CB3 0HF , UK . Email:
Chem Sci. 2019 Nov 13;11(2):435-446. doi: 10.1039/c9sc04589a. eCollection 2020 Jan 14.
Conformationally flexible "Carbene-Metal-Amide" (CMA) complexes of copper and gold have been developed based on a combination of sterically hindered cyclic (alkyl)(amino)carbene (CAAC) and 6- and 7-ring heterocyclic amide ligands. These complexes show photoemissions across the visible spectrum with PL quantum yields of up to 89% in solution and 83% in host-guest films. Single crystal X-ray diffraction and photoluminescence (PL) studies combined with DFT calculations indicate the important role of ring structure and conformational flexibility of the amide ligands. Time-resolved PL shows efficient delayed emission with sub-microsecond to microsecond excited state lifetimes at room temperature, with radiative rates exceeding 10 s. Yellow organic light-emitting diodes (OLEDs) based on a 7-ring gold amide were fabricated by thermal vapor deposition, while the sky-blue to warm-white mechanochromic behavior of the gold phenothiazine-5,5-dioxide complex enabled fabrication of the first CMA-based white light-emitting OLED.
基于空间位阻环状（烷基）（氨基）卡宾（CAAC）与六元环和七元环杂环酰胺配体的组合，已开发出铜和金的构象灵活的“卡宾-金属-酰胺”（CMA）配合物。这些配合物在可见光谱范围内均有光发射，在溶液中的PL量子产率高达89%，在主客体薄膜中的PL量子产率高达83%。单晶X射线衍射和光致发光（PL）研究结合DFT计算表明酰胺配体的环结构和构象灵活性具有重要作用。时间分辨PL显示在室温下具有亚微秒至微秒的激发态寿命的高效延迟发射，辐射速率超过10 s。基于七元环金酰胺的黄色有机发光二极管（OLED）通过热蒸发制备，而金吩噻嗪-5,5-二氧化物配合物的天蓝色至暖白色机械变色行为使得能够制备首个基于CMA的白色发光OLED。
