Turning On the Near-Infrared Photoluminescence of Erbium Metallofullerenes by Covalent Modification
Turning On the Near-Infrared Photoluminescence of Erbium Metallofullerenes by Covalent Modification
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通过共价修饰开启铒金属富勒烯的近红外光致发光
DOI：
10.1021/acs.inorgchem.9b01316
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发表时间：
2019
影响因子：
4.6
通讯作者：
Wang Zhiyong
中科院分区：
文献类型：
--
作者：
Xu Dan;Jiang Yuhang;Wang Yuanyuan;Zhou Tonghui;Shi Zujin;Omachi Haruka;Shinohara Hisanori;Sun Baoyun;Wang Zhiyong
由于富勒烯笼子的猝灭效应，富勒烯中的稀土离子的光致发光通常很弱。在Er@C82的情况下，Er~(3+)离子的近红外发射被C82富勒烯笼完全猝灭。Er@C82和其他单金属富勒烯的光致发光仍然具有挑战性。在这项工作中，我们采用共价修饰策略来改变富勒烯笼子的电子结构，以敏化Er@C2n(2n=72，76和82)金属富勒烯中Er3+离子的近红外发射。经三氟甲基、苯基或二氯苯基共价修饰后，Er金属富勒烯在1.5μm处表现出光致发光，这是Er~(3+)离子的特征发射。特别地，利用该策略将原本无荧光的金属富勒烯Er@C82转化为荧光衍生物。Er~(3+)离子的光致发光归因于从富勒烯笼到Er~(3+)离子的能量转移。根据理论计算，Er~(3+)被富勒烯笼敏化与金属富勒烯衍生物具有较大的HOMO-LUMO能隙和闭壳层电子结构有关。本工作为新型荧光金属富勒烯的设计和合成提供了有益的指导。
The photoluminescence of lanthanide ions inside fullerenes is usually very weak due to the quenching effect of the fullerene cage. In the case of Er@C82, the near-infrared emission from the Er3+ion is completely quenched by the C82fullerene cage. It remains challenging to turn on the photoluminescence of Er@C82and other monometallofullerenes. In this work, we adopt a covalent modification strategy to alter the electronic structure of the fullerene cage for sensitizing the near-infrared emission of Er3+ions in metallofullerenes Er@C2n(2n= 72, 76, and 82). After covalent modification with trifluoromethyl, phenyl, or dichlorophenyl groups, the erbium metallofullerenes exhibit photoluminescence at 1.5 μm, which is the characteristic emission of the Er3+ion. Particularly, the otherwise nonfluorescent metallofullerene Er@C82is transformed into fluorescent derivatives by using this strategy. The photoluminescence from the Er3+ion is ascribed to energy transfer from the fullerene cage to the Er3+ion. According to theoretical calculations, the sensitization of the Er3+ion by the fullerene cage is associated with the large HOMO–LUMO gap and the closed-shell electronic structure of the metallofullerene derivatives. This work provides useful guidance for the design and synthesis of new fluorescent metallofullerenes.