State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University , Changchun 130012, People's Republic of China.
Division of Physical Sciences and Engineering, KAUST Solar Center, King Abdullah University of Science and Technology (KAUST) , Thuwal 23955-6900, Saudi Arabia.
J Am Chem Soc. 2017 Mar 29;139(12):4318-4321. doi: 10.1021/jacs.7b00773. Epub 2017 Mar 20.
Aggregation/assembly induced emission (AIE) has been observed for metal nanoclusters (NCs), but the origin of the enhanced emission is not fully understood, yet. In this work, the significant contribution of metal defects on AIE is revealed by engineering the self-assembly process of Cu NCs using ethanol. The presence of ethanol leads to a rapid assembly of NCs into ultrathin nanosheets, promoting the formation of metal defects-rich surface. Detailed studies and computer simulation confirm that the metal defects-rich nanosheets possess increased Cu(I)-to-Cu(0) ratio, which greatly influences ligand-to-metal-metal charge transfer and therewith facilitates the radiative relaxation of excitons. Consequently, the Cu NCs self-assembly nanosheets exhibit obvious emission enhancement.
聚集/组装诱导发光（AIE）已在金属纳米团簇（NCs）中观察到，但增强发光的起源尚未完全理解。在这项工作中，通过使用乙醇工程化 Cu NCs 的自组装过程，揭示了金属缺陷对 AIE 的重要贡献。乙醇的存在导致 NCs 快速组装成超薄纳米片，促进了富含金属缺陷的表面的形成。详细的研究和计算机模拟证实，富含金属缺陷的纳米片具有增加的 Cu(I)-to-Cu(0) 比例，这极大地影响了配体-金属-金属电荷转移，从而促进了激子的辐射弛豫。因此，Cu NCs 自组装纳米片表现出明显的发射增强。
