Interfacial Clustering-Triggered Fluorescence-Phosphorescence Dual Solvoluminescence of Metal Nanoclusters
Interfacial Clustering-Triggered Fluorescence-Phosphorescence Dual Solvoluminescence of Metal Nanoclusters
复制标题
金属纳米团簇的界面团簇触发荧光-磷光双溶剂发光
DOI：
10.1021/acs.jpclett.7b01736
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发表时间：
2017
影响因子：
5.7
通讯作者：
Xu Jianhua
中科院分区：
文献类型：
--
作者：
Yang Taiqun;Dai Shan;Yang Songqiu;Chen Li;Liu Pengcheng;Dong Kailong;Zhou Jiasheng;Chen Yuting;Pan Haifeng;Zhang Sanjun;Chen Jinquan;Zhang Kun;Wu Peng;Xu Jianhua
采用简单的溶剂激发策略，成功地实现了水溶性金属纳米团簇在室温下的荧光-磷光双溶剂发光。羧酸配体和金属核在纳米级界面处的强相互作用不仅诱导了羰基的刚性构象，而且还提供了完美的羰基簇，其作为金属NC的精确发色团用于聚集诱导发射（AIE）机制。新发现的n → π* 非共价相互作用促进了聚合物主链上羰基的成簇。聚合物团簇中强的n → π* 相互作用引发相邻羰基之间重叠的C → O双键中电子的有效离域，解释了其独特的SL性质，特别是异常磷光。这进一步证实了控制实验的存在下，系统间交叉（ISC）的过渡。研究结果为理解复杂的光致发光过程提供了新的视角，拓宽了金属纳米材料的应用范围，为研究光致发光的内在机理开辟了新的途径。
The fluorescence–phosphorescence dual solvoluminescence (SL) of water-soluble metal nanoclusters (NCs) at room temperature was successfully achieved by a simple solvent-stimulated strategy. The strong interaction between carboxylate ligands and the metal core at the nanoscale interface not only induces rigid conformations of carbonyl groups but also affords a perfect carbonyl cluster that acts as an exact chromophore of metal NCs for aggregation-induced emission (AIE) mechanics. The clustering of carbonyl groups bearing on the polymer backbone chain is promoted by newly discovered n → π* noncovalent interactions. The efficient delocalization of electrons in overlapped CO double bonds between neighboring carbonyl groups triggered by strong n → π* interactions in the polymer cluster accounts for its unique SL properties, especially the abnormal phosphorescence. This was further confirmed by controlled experiments for the presence of intersystem crossing (ISC) transitions. The results provide novel insights for understanding the complex SL process and open up a new way to study the inherent mechanism of SL by broadening the application of metal NCs.