Ion Site Substitution in a Sulfonylcalix[4]arene-Supported Ln8 (Ln = Tb and Eu) Coordination Wheel with Tunable Luminescence

IF 3.2 2区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

Crystal Growth & Design Pub Date : 2024-09-20 DOI:10.1021/acs.cgd.4c00682

Linmeng Xu, Tianxia Chen, Kun Zhou, Baokuan Chen, Yanfeng Bi

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Abstract

Lanthanide coordination clusters (LCCs), namely, [Ln₈(TC4A-SO₂)₄(TA)₂(DMF)₄(H₂O)₁₀] (solvents) (Ln₈ = Tb₈, Eu₈, Tb₄Eu₄; H₄TC4A-SO₂ = p-tert-butylsulfonylcalix[4]arene; H₄TA = dl-tartaric acid), were synthesized via the solvothermal method and were characterized by single-crystal X-ray diffraction. Ln₈ is a wheel-shaped framework built from four cone-shaped mononuclear units (Ln^III-TC4A-SO₂) and four bridging-Ln^III ions with two tartrates located in the center serving as “spokes”. Tb₈ exhibits an extraordinary luminescence quantum yield (QY_s) of 53.3% in the solid state under the excitation of 370 nm, while Eu₈ cannot emit under similar conditions. Furthermore, Tb₈ shows concentration-dependent emission in a methanol solution with the best luminescence QY_l of 61.8%, representing one of the best luminescent Tb-based coordination clusters. The Eu ions can be rationally doped in the Tb ring (Tb_xEu_8–x, 4 ≤ x < 8) by a stoichiometric ratio on specific sites to tune the emission color output, which reveals the efficient energy transfer from ⁵D₄-⁷F₅ and ⁵D₄-⁷F₆ levels of Tb^III to the ⁵D₀ level of Eu^III. This work presents a unique method of controlling the fabrication and tunable luminescence of LCCs.

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可调谐发光的磺酰基钙[4]炔支撑 Ln8（Ln = Tb 和 Eu）配位轮中的离子位点置换

镧系元素配位团（LCC），即[Ln8(TC4A-SO2)4(TA)2(DMF)4(H2O)10]（溶剂）（Ln8 = Tb8, Eu8, Tb4Eu4; H4TC4A-SO2 = p-ter-butylsulfonylcalix[4]arene；H4TA = dl-酒石酸），并通过单晶 X 射线衍射进行了表征。Ln8 是由四个锥形单核单元（LnIII-TC4A-SO2）和四个桥接的 LnIII 离子构成的轮状框架，中间的两个酒石酸盐充当 "辐条"。在 370 纳米的激发下，Tb8 在固态下显示出 53.3% 的非凡发光量子产率（QYs），而 Eu8 在类似条件下无法发光。此外，Tb8 在甲醇溶液中显示出浓度依赖性发射，最佳发光量子产率为 61.8%，是最佳发光铽基配位团簇之一。Eu离子可以按化学计量比合理地掺杂在Tb环（TbxEu8-x，4 ≤ x <8）的特定位点上，以调节发射色输出，这揭示了从TbIII的5D4-7F5和5D4-7F6电平到EuIII的5D0电平的高效能量转移。这项研究提出了一种独特的方法来控制 LCC 的制造和可调发光。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Crystal Growth & Design 化学-材料科学：综合

CiteScore

6.30

自引率

10.50%

发文量

650

审稿时长

1.9 months

期刊介绍： The aim of Crystal Growth & Design is to stimulate crossfertilization of knowledge among scientists and engineers working in the fields of crystal growth, crystal engineering, and the industrial application of crystalline materials. Crystal Growth & Design publishes theoretical and experimental studies of the physical, chemical, and biological phenomena and processes related to the design, growth, and application of crystalline materials. Synergistic approaches originating from different disciplines and technologies and integrating the fields of crystal growth, crystal engineering, intermolecular interactions, and industrial application are encouraged.