Synthesis and Properties Evolution of a Family of Tiara-like Phenylethanethiolated Palladium Nanoclusters.
Synthesis and Properties Evolution of a Family of Tiara-like Phenylethanethiolated Palladium Nanoclusters.
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一类Tiara类苯基乙硫醇化钯纳米团簇的合成及性能演化
DOI：
10.1038/srep16628
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发表时间：
2015-11-16
影响因子：
4.6
通讯作者：
Wu Z
中科院分区：
文献类型：
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作者：
Chen J;Liu L;Weng L;Lin Y;Liao L;Wang C;Yang J;Wu Z
过渡金属(镍、钯、铂)纳米簇合物由于其基础科学意义和在许多领域的潜在应用而引起人们的广泛兴趣。然而，到目前为止，由于获得一系列纳米团簇类似物的挑战，随着环尺寸的增加，性质(例如吸收)的演变还没有得到研究。在这里，我们成功地合成、分离和鉴定了一族[Pd(SC2H4Ph)2]n纳米簇合物(共17个新簇合物，n = 4-20)。通过单晶X-射线衍射学和理论计算确定了它们的结构为冠状结构，并根据实验观察提出了它们的形成机理为取代-缩聚-闭环过程。所有这些簇都是相当健壮的(抗还原和抗氧化)，这是因为它们的头饰状结构具有较大的HOMO-LUMO间隙。最后，研究了[Pd(SR)2]n纳米团簇的光学和电化学演化过程，发现对于[Pd(SR)2]n纳米团簇，光学能隙和电化学能隙都有一个“转折点”，其尺寸对应于n = 8。
Tiara-like thiolated group 10 transition metal (Ni, Pd, Pt) nanoclusters have attracted extensive interest due to their fundamental scientific significance and potential application in a number of fields. However, the properties (e.g.the absorption) evolution with the ring size’s increase was not investigated so far to our best knowledge, due to the challenge of obtaining a series of nanocluster analogues. Herein, we successfully synthesized, isolated and identified a family of [Pd(SC2H4Ph)2]nnanoclusters (totally 17 novel clusters, n = 4–20). Their structures were determined to be tiara-like by single crystal X-ray crystallography together with theoretical calculation; their formation mechanism was proposed to be a substitution—polycondensation—ring-closure process based on experimental observations. All of these clusters are rather robust (anti-reductive and anti-oxidative) owing to their tiara-like structures with large HOMO-LUMO gaps. Finally, the optical and electrochemical evolution with the increase of ring size was investigated and it is found that both optical and electrochemical gaps have a “turning point” at a size corresponding to n = 8 for [Pd(SR)2]nnanoclusters.