Cao Yitao, Fung Victor, Yao Qiaofeng, Chen Tiankai, Zang Shuangquan, Jiang De-En, Xie Jianping
Department of Chemical and Biomolecular Engineering, National University of Singapore, 4 Engineering Drive 4, Singapore, 117585, Singapore.
Department of Chemistry, University of California, Riverside, CA, 92521, USA.
Nat Commun. 2020 Oct 30;11(1):5498. doi: 10.1038/s41467-020-19327-2.
Diverse methods have been developed to tailor the number of metal atoms in metal nanoclusters, but control of surface ligand number at a given cluster size is rare. Here we demonstrate that reversible addition and elimination of a single surface thiolate ligand (-SR) on gold nanoclusters can be realized, opening the door to precision ligand engineering on atomically precise nanoclusters. We find that oxidative etching of [AuSR] nanoclusters adds an excess thiolate ligand and generates a new species, [AuSR]. The addition reaction can be reversed by CO reduction of [AuSR], leading back to [AuSR] and eliminating precisely one surface ligand. Intriguingly, we show that the ligand shell of Au nanoclusters becomes more fragile and rigid after ligand addition. This reversible addition/elimination reaction of a single surface ligand on gold nanoclusters shows potential to precisely control the number of surface ligands and to explore new ligand space at each nuclearity.
人们已经开发出多种方法来调整金属纳米团簇中金属原子的数量，但在给定团簇尺寸下控制表面配体数量的情况却很少见。在此，我们证明了金纳米团簇上单个表面硫醇盐配体（-SR）的可逆添加和消除是可以实现的，这为原子精确纳米团簇的精确配体工程打开了大门。我们发现，[AuSR]纳米团簇的氧化蚀刻会添加过量的硫醇盐配体并生成一种新物质[AuSR]。通过[AuSR]的CO还原可以使添加反应逆转，回到[AuSR]并精确消除一个表面配体。有趣的是，我们表明金纳米团簇的配体壳在添加配体后变得更脆弱和更刚性。金纳米团簇上单个表面配体的这种可逆添加/消除反应显示出精确控制表面配体数量以及在每个核数下探索新配体空间的潜力。
