Zhang Kun, Lu Ze-Ying, Feng Cheng-Cheng, Yang Zhuo-Ran, Nie Peng-Peng, Chen Ting-Ting, Zhang Lin-Feng, Ma Shuang, Shen Yin-Jing, Lin Meng-Lu
Department of Chemistry, Zhejiang Sci-Tech University, Xiasha Higher Education District, Hangzhou 310018, P. R. China.
ACS Omega. 2019 Oct 23;4(19):18334-18341. doi: 10.1021/acsomega.9b02576. eCollection 2019 Nov 5.
Here, we report our trials to regulate the luminescence performance of the macrocyclic samarium(III) complex and prepare four excellent luminescent Sm(III) complex-doped poly(methylmethacrylate) (PMMA) composites. Four 23-membered [1 + 1] Schiff-base macrocyclic mononuclear Sm(III) complexes, - , originating from dialdehydes with different pendant arms and 1,2-bis(2-aminoethoxy)ethane, have been constructed by the template method. Crystal structures reveal that every Sm(III) ion with the coordination geometry of a distorted bicapped square antiprism is capsulated by the macrocyclic cavity environment forming the "lasso-type" protection. Relative photophysical properties of macrocyclic Sm(III) complexes are carefully investigated in solid-state, methanol solution, and doped PMMA film, and all these show characteristic emissions of the Sm(III) ion associated with satisfactory lifetimes and quantum yields in all media, which could be comparable to reported outstanding examples. Especially, the luminescence performance for this type of Sm(III) complex could be regulated in the solid state by the use of different functional groups in the pendant arm while it is not achieved in solution and the doped PMMA composite. High emitting and air-stable plastic materials could be obtained when these Sm(III) complexes are doped in PMMA with 0.1 wt % mixing ratio, and the corresponding maximum lifetime and quantum yield are 61.2 μs and 0.63% in the case of complex , respectively. We believe that these highly luminescent "lasso-type" Sm(III) complexes and doped PMMA composites are valuable references in the design of luminescent lanthanide(III) hybrid materials.
在此，我们报告了调节大环钐（III）配合物发光性能的试验，并制备了四种优异的发光钐（III）配合物掺杂聚甲基丙烯酸甲酯（PMMA）复合材料。通过模板法构建了四种源自具有不同侧链臂的二醛和1,2 - 双（2 - 氨基乙氧基）乙烷的23元[1 + 1]席夫碱大环单核钐（III）配合物， - 。晶体结构表明，每个具有扭曲双帽四方反棱柱配位几何构型的钐（III）离子被大环腔环境包裹，形成“套索型”保护。对大环钐（III）配合物在固态、甲醇溶液和掺杂PMMA薄膜中的相对光物理性质进行了仔细研究，所有这些都显示出钐（III）离子的特征发射，在所有介质中具有令人满意的寿命和量子产率，这与已报道的优秀实例相当。特别是，这类钐（III）配合物的发光性能在固态下可通过侧链臂中不同官能团来调节，而在溶液和掺杂PMMA复合材料中则无法实现。当这些钐（III）配合物以0.1 wt%的混合比例掺杂在PMMA中时，可获得高发光且空气稳定的塑料材料，对于配合物 ，相应的最大寿命和量子产率分别为61.2 μs和0.63%。我们认为，这些高发光的“套索型”钐（III）配合物和掺杂PMMA复合材料在发光镧系（III）杂化材料的设计中具有重要参考价值。
