A mono-copper doped undeca-gold cluster with up-converted and anti-stokes emissions of fluorescence and phosphorescence.
A mono-copper doped undeca-gold cluster with up-converted and anti-stokes emissions of fluorescence and phosphorescence.
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DOI：
10.1039/d0nr07624d
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发表时间：
2021-03
期刊：
影响因子：
6.7
通讯作者：
Haiming Wu;Ye-guang Fang;Rajini Anumula;G. N. Andrew;G. Cui;Weihai Fang;Zhixun Luo;J. Yao
中科院分区：
文献类型：
--
作者：
Haiming Wu;Ye-guang Fang;Rajini Anumula;G. N. Andrew;G. Cui;Weihai Fang;Zhixun Luo;J. Yao
We have synthesized single crystals of a highly stable Cu-doped undeca-gold cluster protected by both triphenylphosphine (PPh3) and 2-pyridinethiol (-SPy) ligands, formulated as [Au11Cu1(PPh3)7(SPy)3]+. This cluster (Au11Cu1 NCs for short) has a metallic core of C3v Au@Au10 with the Cu atom capped on one of the nine triangular facets and it is triply-coordinated to three N atoms of the SPy ligands of which the sulfur atom simultaneously binds to three adjacent Au atoms via singly-coordinated S-Au bonds, respectively. The other seven gold atoms form a crown structure by a link of three orthogons with common sides and are protected by seven PPh3 ligands. Besides the well-organized coordination, this Au11Cu1 nanocluster is demonstrated to exhibit superatom stability of the metallic core within 8 valence electrons (assuming that the 3 electrophilic-SPy ligands capture 3 electrons from the metal center). More interestingly, this Au11Cu1 nanocluster shows interesting emissions in both ultraviolet visible (UV-Vis) and near infrared (NIR) regions, and the emissions display novel anti-Stokes up-conversion lasing characteristics. TD-DFT calculated UV-vis and emission spectra well reproduce the experimental results, shedding light on the nature of excitation states and underlying mechanism of electronic transitions between diverse energy levels of such a monolayer-protected bimetallic cluster.
