Binuclear complexes of lanthanide pivalates with triethanolamine demonstrate a step-wise ligand loss and switching of photoluminescence properties

IF 4.2 3区材料科学 Q2 MATERIALS SCIENCE, MULTIDISCIPLINARY

Optical Materials Pub Date : 2025-08-23 DOI:10.1016/j.optmat.2025.117438

Irina Sabitova, Dmitry Tsymbarenko

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Abstract

New mixed-ligand binuclear complexes [Ln₂(TeaH₂)(TeaH₃)(Piv)₅]∙H₂O·CH₃CN (Eu∙CH₃CN·H₂O) and [Ln₂(TeaH₂)₂(Piv)₄] (Gd, Tb) were synthesized by direct reaction of lanthanide pivalates (Piv^–, 2,2-dimethylpropanoate) with triethanolamine (TeaH₃) and characterized by single crystal and powder XRD, FTIR, TGA and luminescence spectroscopy. Triethanolamine appears as chelating-bridging anionic (TeaH₂^–) and as chelating neutral (TeaH₃) ligand. Two types of mixed-metal solid solutions [(Eu_1-xTb_x)₂(TeaH₂)(TeaH₃)(Piv)₅]∙H₂O·CH₃CN (x = 0.02) and [(Eu_1-xTb_x)₂(TeaH₂)₂(Piv)₄] (x = 0.19–0.95) form depending on the Eu/Tb ratio. The TGA and VT-PXRD reveal a loss of ethyl pivalate fragment upon heating at 200 °C. Transformation of binuclear [(Eu_1-xTb_x)₂(TeaH₂)₂(Piv)₄] into intermediate [(Eu_1-xTb_x)₂(TeaH₂)(Piv)₃(TeaH₂^-C2H5)]_n at 200 °C leads to ‘switching off’ of Tb-centered photoluminescence, sharp increase of LIR and relative temperature sensitivity S_r as high as 722 %/°C for x = 0.68.

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镧系酸盐与三乙醇胺的双核配合物表现出配体的逐步损失和光致发光性质的切换

以三乙醇胺（TeaH3）为原料，以Piv -， 2,2-二甲基丙酸镧系酯为原料，直接反应合成了新型混合配体双核配合物[Ln2(TeaH2)(TeaH3)(Piv)5]∙H2O·CH3CN （Eu∙CH3CN·H2O）和[Ln2(TeaH2)2(Piv)4] (Gd, Tb)，并采用单晶、粉末XRD、FTIR、TGA和发光光谱对其进行了表征。三乙醇胺表现为螯合桥接阴离子（TeaH2 -）和螯合中性（TeaH3）配体。两种类型的混合金属固溶体[(Eu1-xTbx)2(TeaH2)(TeaH3)(Piv)5]∙H2O·CH3CN （x = 0.02）和[(Eu1-xTbx)2(TeaH2)2(Piv)4] （x = 0.19-0.95）取决于Eu/Tb比。TGA和VT-PXRD分析表明，在200℃加热时，戊酸乙酯片段丢失。双核[(Eu1-xTbx)2(TeaH2)2(Piv)4]在200℃下转化为中间体[(Eu1-xTbx)2(TeaH2)(Piv)3(TeaH2- c2h5)]n，导致tb中心光致发光“关闭”，LIR急剧增加，相对温度灵敏度Sr高达722% /℃，x = 0.68。

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来源期刊

Optical Materials 工程技术-材料科学：综合

CiteScore

6.60

自引率

12.80%

发文量

1265

审稿时长

38 days

期刊介绍： Optical Materials has an open access mirror journal Optical Materials: X, sharing the same aims and scope, editorial team, submission system and rigorous peer review. The purpose of Optical Materials is to provide a means of communication and technology transfer between researchers who are interested in materials for potential device applications. The journal publishes original papers and review articles on the design, synthesis, characterisation and applications of optical materials. OPTICAL MATERIALS focuses on: • Optical Properties of Material Systems; • The Materials Aspects of Optical Phenomena; • The Materials Aspects of Devices and Applications. Authors can submit separate research elements describing their data to Data in Brief and methods to Methods X.