Lu Zixiu, Wang Shujian, Zhuo Zhu, Li Guo-Ling, Zhu Haomiao, Wang Wei, Huang You-Gui, Hong Maochun
School of Rare Earth, University of Science and Technology of China Ganzhou China.
Ganjiang Innovation Academy, Chinese Academy of Sciences Ganzhou 341000 China.
RSC Adv. 2022 Oct 12;12(45):29151-29161. doi: 10.1039/d2ra04942b. eCollection 2022 Oct 11.
Luminescence stability is a critical consideration for applying phosphors in practical devices. In this work, we report two categories of double -butylthiacalix[4]arene (HTC4A) capped clusters that exhibit characteristic lanthanide luminescence. Specifically, {[Ln(μ-OH)(TC4A)(DMF)(CHOH)(HCOO)Cl]}·CHOH (Ln = Eu (1), Tb (2); = 0-1) with square-planar [Ln(μ-OH)] cluster cores and {[Ln(μ-OH)(μ-OH)(OCH) (TC4A) (HO)Cl]}·DMF (Ln = Gd (3), Tb (4), Dy (5); = 2-6) with hourglass-like [Ln(μ-OH)(μ-OH)] cluster cores are synthesized and characterized. By comparing 2 and 4, we find that several critical luminescence properties (such as quantum efficiency and luminescence stabilities) depend directly on the cluster core structure. With the square-planar [Ln(μ-OH)] cluster cores, 2 demonstrates high quantum yield (∼65%) and excellent luminescence stability against moisture, high temperature, and UV-radiation. A white light-emitting diode (LED) with ultrahigh color quality is successfully fabricated by mixing 2 with commercial phosphors. These results imply that high quality phosphors might be achieved by exploiting the double thiacalix[4]arene-capping strategy, with an emphasis on the cluster core structure.
发光稳定性是将磷光体应用于实际器件时的一个关键考量因素。在这项工作中，我们报道了两类由双丁基硫杂杯[4]芳烃（HTC4A）包覆的簇合物，它们展现出镧系元素的特征发光。具体而言，合成并表征了具有平面正方形[Ln(μ-OH)]簇核的{[Ln(μ-OH)(TC4A)(DMF)(CHOH)(HCOO)Cl]}·CHOH（Ln = Eu (1)，Tb (2)； = 0 - 1）以及具有沙漏状[Ln(μ-OH)(μ-OH)]簇核的{[Ln(μ-OH)(μ-OH)(OCH)(TC4A)(HO)Cl]}·DMF（Ln = Gd (3)，Tb (4)，Dy (5)； = 2 - 6）。通过比较2和4，我们发现几个关键的发光性质（如量子效率和发光稳定性）直接取决于簇核结构。对于具有平面正方形[Ln(μ-OH)]簇核的2，它表现出高量子产率（约65%）以及在防潮、高温和紫外线辐射方面优异的发光稳定性。通过将2与商用磷光体混合，成功制备出了具有超高色质的白色发光二极管（LED）。这些结果表明，通过采用双硫杂杯[4]芳烃包覆策略，特别是关注簇核结构，有可能实现高质量的磷光体。
