Preparation of a Lanthanide-Titanium Oxo Cluster-Polymer Composite by CuI-Catalyzed Click Chemistry
Preparation of a Lanthanide-Titanium Oxo Cluster-Polymer Composite by CuI-Catalyzed Click Chemistry
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DOI：
10.1002/chem.202004457
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发表时间：
2020-12-09
影响因子：
4.3
通讯作者：
Zheng, Lan-Sun
中科院分区：
文献类型：
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作者：
Deng, Yong-Kai;Zhao, Ya-Rui;Zheng, Lan-Sun
通过点击反应将金属团簇嵌入有机聚合物骨架中，不仅可以有效地制备团簇-聚合物复合材料，而且可以有效地避免团簇聚集。在此，Eu 8 Ti 10-N-3的含叠氮化物镧系元素-钛氧代簇合物（Eu 8 Ti 10-N-3=[Eu 8 Ti 10（mu（3）-O）（14）（H2O）（4）（OAc）（2）（tbba）（30）（paza）（4）（THF）（2）]·4THF·8H 2 O（1），Htbba=4-叔丁基苯甲酸，Hpaza=4-叠氮基苯甲酸酯，HOAc=乙酸，THF=四氢呋喃）通过4-叠氮基苯甲酸和4-叔丁基苯甲酸的原位溶剂热反应。1与PEG（PEG=甲氧基聚（乙二醇）炔，2000 g mol（-1））通过Cu-I催化的点击化学反应生成Eu 8 Ti 10-N-3@PEG的镧系元素-聚合物复合物（2）。2的IR、H-1 NMR和ICP-OES研究表明，1的结构完整性在2中得以保持。对1和2的发光性质的研究表明，1本身的量子产率在2中基本保持不变。值得注意的是，2的形成不仅可以有效地防止簇1聚集，而且还大大提高了其溶解性和对基底的粘附性。由于发光材料的溶解性和粘附性是其实际应用的关键，因此本工作对金属簇-聚合物复合发光材料的发展具有重要意义。
Incorporating metal clusters within the skeleton of the organic polymers through a click reaction cannot only effectively prepare cluster-polymer composites, but also effectively avoid the cluster aggregation. Herein, an azide-containing lanthanide-titanium oxo cluster of Eu8Ti10-N-3 (Eu8Ti10-N-3=[Eu8Ti10(mu(3)-O)(14)(H2O)(4)(OAc)(2)(tbba)(30)(paza)(4)(THF)(2)].4 THF.8 H2O (1), Htbba=4-tert-butylbenzoic acid, Hpaza=4-azidobenzoate, HOAc=acetic acid, THF=tetrahydrofuran) through an in situ solvothermal reaction of 4-azidobenzoic acid and 4-tert-butylbenzoic acid. Reaction of 1 with PEG (PEG=methoxypoly(ethyleneglycol)alkyne, 2000 g mol(-1)) through Cu-I-catalyzed click chemistry generates a lanthanide-polymer composite of Eu8Ti10-N-3@PEG (2). Investigation with IR, H-1 NMR and ICP-OES of 2 indicates that the structural integrity of 1 is maintained in 2. Study of the luminescent properties of 1 and 2 reveals that the quantum yield of 1 itself basically remains unchanged in 2. Significantly, the formation of 2 cannot only effectively prevent the cluster 1 from aggregation, but also greatly enhance its solubility and adhesion to the substrate. Owing to the solubility and adhesion of luminescent materials being the key to their practical application, present work is thus of great significance for the development of metal cluster-polymer composite luminescent materials.