Application of NHC-modified Gold Nanoclusters in Photoredox Catalysis

NHC修饰金纳米团簇在光氧化还原催化中的应用

基本信息

批准号：
20F20329
负责人：
CRUDDEN Cathleen
金额：
$ 1.41万
依托单位：
Nagoya University
依托单位国家：
日本
项目类别：
Grant-in-Aid for JSPS Fellows
财政年份：
2020
资助国家：
日本
起止时间：
2020-11-13 至 2023-03-31
项目状态：
已结题

项目摘要

N-heterocyclic carbenes (NHCs) have recently emerged as valuable alternatives to thiols or phosphines for the stabilization of metal surfaces, nanoparticles, and clusters. The neutral, electron-rich NHCs form a strong covalent bond with the metal, which is important in providing stability to metal nanoclusters.Thus far we have been able to synthesize a series of chiral Au13 nanoclusters via the direct reduction of achiral dinuclear Au(I) halide complexes ligated by ortho-xylyl-linked bis-N-heterocyclic carbene (bisNHC) ligands. A broad range of functional groups are tolerated as wingtip substituents, allowing for the synthesis of a variety of functionalized chiral Au13 nanoclusters. We have used single-crystal X-ray crystallography to confirm the molecular formula to be [Au13(bisNHC)5Cl2]Cl3, with a chiral helical arrangement of the five bidentate NHC ligands around the icosahedral Au13 core. This Au13 nanocluster is highly luminescent, with a quantum yield of 23%. The two enantiomers of the Au13 clusters can be separated by chiral HPLC, and the isolated enantiomers characterized by circular dichroism spectroscopy. The clusters synthesized by us show remarkable stability, including configurational stability, opening the door to further investigation of the effect of chirality on these clusters. Our preliminary results showed that this bisNHC Au13 nanocluster is friendly to cells and can be used for the cell imaging.

N-杂环卡宾斯（NHC）最近已成为金属表面，纳米颗粒和簇稳定的硫醇或磷的宝贵替代品。 The neutral, electron-rich NHCs form a strong covalent bond with the metal, which is important in providing stability to metal nanoclusters.Thus far we have been able to synthesize a series of chiral Au13 nanoclusters via the direct reduction of achiral dinuclear Au(I) halide complexes ligated by ortho-xylyl-linked bis-N-heterocyclic carbene （BISNHC）配体。广泛的官能团被耐受为机翼取代基，可以合成各种官能化的手性AU13纳米簇。我们已经使用了单晶X射线晶体学来确认分子公式为[Au13（BisnHC）5Cl2] Cl3，并具有五个BIDENATE NHC配体周围的五个BIDENATE NHC配体的手性螺旋排列。该AU13纳米簇具有高度发光，量子产率为23％。 Au13簇的两个对映异构体可以通过手性HPLC分离，并且以圆形二科主义光谱为特征的分离的对映异构体。美国合成的簇显示出了显着的稳定性，包括配置稳定性，为进一步研究手性对这些簇的影响打开了大门。我们的初步结果表明，这种BisnHC Au13纳米簇对细胞友好，可用于细胞成像。