Host-Guest Chemistry in Boron Nitride Nanotubes: Interactions with Polyoxometalates and Mechanism of Encapsulation.
Host-Guest Chemistry in Boron Nitride Nanotubes: Interactions with Polyoxometalates and Mechanism of Encapsulation.
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DOI：
10.1021/jacs.2c10961
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发表时间：
2023-01-18
影响因子：
15
通讯作者：
Khlobystov, Andrei N.
中科院分区：
文献类型：
--
作者：
Jordan, Jack W.;Chernov, Alexander, I;Rance, Graham A.;Davies, E. Stephen;Lanterna, Anabel E.;Fernandes, Jesum Alves;Gruneis, Alexander;Ramasse, Quentin;Newton, Graham N.;Khlobystov, Andrei N.
氮化硼纳米管(BNNTs)是一类新兴的分子容器，为在纳米尺度上研究分子提供了新的功能和可能性。在这里，BNNTs被证明是多金属氧酸盐(POM)分子的高效纳米容器。在室温下，POM在BNNTs中的包覆自发地发生在水溶液中，导致了POM@BNNT主客体系统的自组装。对主体-纳米管和客体分子相互作用的分析表明，POM(碱)的W=O基团和BNNT晶格(酸)的B-原子之间的Lewis酸碱相互作用可能是推动POM包覆的主要原因，溶液中BNNTs到POMS的光活化电子转移也起到了作用。BNNT纳米容器的透明性质允许通过光致发光、拉曼、UV-Vis吸收和EPR光谱对客体分子进行广泛的研究。这些研究揭示了BNNTs和POMS之间相当大的能量和电子转移过程，可能是通过BNNTs的缺陷能态，导致BNNT的室温光致发光猝灭，在低温(<；100K)下出现新的光致发光发射，光致变色反应，以及来自客体POMS的顺磁信号。这些现象为纳米尺度上的主客体相互作用提供了一个新的视角，并为获取这些杂交系统的功能特性提供了开放的途径。
Boron nitride nanotubes (BNNTs) are an emerging class of molecular container offering new functionalities and possibilities for studying molecules at the nanoscale. Herein, BNNTs are demonstrated as highly effective nanocontainers for polyoxometalate (POM) molecules. The encapsulation of POMs within BNNTs occurs spontaneously at room temperature from an aqueous solution, leading to the self-assembly of a POM@BNNT host–guest system. Analysis of the interactions between the host-nanotube and guest-molecule indicate that Lewis acid–base interactions between W=O groups of the POM (base) and B-atoms of the BNNT lattice (acid) likely play a major role in driving POM encapsulation, with photoactivated electron transfer from BNNTs to POMs in solution also contributing to the process. The transparent nature of the BNNT nanocontainer allows extensive investigation of the guest-molecules by photoluminescence, Raman, UV–vis absorption, and EPR spectroscopies. These studies revealed considerable energy and electron transfer processes between BNNTs and POMs, likely mediated via defect energy states of the BNNTs and resulting in the quenching of BNNT photoluminescence at room temperature, the emergence of new photoluminescence emissions at cryogenic temperatures (<100 K), a photochromic response, and paramagnetic signals from guest-POMs. These phenomena offer a fresh perspective on host–guest interactions at the nanoscale and open pathways for harvesting the functional properties of these hybrid systems.
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影响因子：
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作者：
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