Sun Jing, Tang Xiongkai, Tang Jiaqi, Zhang Yuhao, Li Zilin, Guo Shuo, Shen Hui
College of Energy Materials and Chemistry, Inner Mongolia University, Hohhot 010021, China.
Inner Mongolia Key Laboratory of Fine Organic Synthesis, Department of Chemistry and Chemical Engineering, College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021, China.
Inorg Chem. 2023 Apr 3;62(13):5088-5094. doi: 10.1021/acs.inorgchem.2c04200. Epub 2023 Mar 22.
Little advance has been made toward developing alternative bottom-up synthetic strategies for -heterocyclic carbene (NHC)-stabilized gold nanoclusters, although this unique class of nanomaterials has exhibited exciting properties. We report in this work a simple and straightforward approach toward NHC-ligated gold nanoclusters by using imidazolium salts rather than free carbenes or NHC-coordinated gold complexes (NHC-Au-X, X is counterions) as precursors. Illustrated here is a one-pot and one-step preparation of an NHC-stabilized AuBr cluster that features a distinct molecular formula, surface motifs, and assembling modes chemical reduction of dpaAu, NaOMe, and NHC·HBr by NaBH (Hdpa is dipyridylamine; NHC·HBr is 1,3-dibenzyl-5,6-difluoro-1-benzo[]imidazole-3-ium bromide). UV-vis and NMR studies have elucidated the base-assisted formation of NHCs from imidazolium salts for the protection of the metal core. This work not only reports a new NHC-ligated superatom that completes the Au library, thus facilitating structure-property studies, but also opens the door to explore underlying analogues in a facile and reasonable way.
尽管这类独特的纳米材料展现出了令人兴奋的特性，但在开发用于氮杂环卡宾（NHC）稳定的金纳米团簇的自下而上的替代合成策略方面进展甚微。我们在这项工作中报道了一种简单直接的方法来制备NHC连接的金纳米团簇，该方法使用咪唑盐而非游离卡宾或NHC配位的金配合物（NHC-Au-X，X为抗衡离子）作为前体。本文展示了一种一锅一步法制备NHC稳定的AuBr团簇的方法，其具有独特的分子式、表面基序和组装模式——通过NaBH4对dpaAu、NaOMe和NHC·HBr进行化学还原（Hdpa为二吡啶胺；NHC·HBr为1,3-二苄基-5,6-二氟-1-苯并[]咪唑-3-鎓溴化物）。紫外可见光谱和核磁共振研究阐明了由咪唑盐通过碱辅助形成NHC以保护金属核的过程。这项工作不仅报道了一种新的NHC连接的超原子，完善了金的体系，从而促进结构-性能研究，还为以简便合理的方式探索潜在类似物打开了大门。
