The tetrahedral structure and luminescence properties of Bi-metallic Pt(1)Ag(28)(SR)(18)(PPh(3))(4) nanocluster.
The tetrahedral structure and luminescence properties of Bi-metallic Pt(1)Ag(28)(SR)(18)(PPh(3))(4) nanocluster.
复制标题
双金属Pt1Ag28(SR)(18)(PPh3)(4)纳米团簇的四面体结构及发光性能
DOI：
10.1039/c6sc05104a
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发表时间：
2017-04-01
期刊：
影响因子：
8.4
通讯作者：
Jin R
中科院分区：
文献类型：
--
作者：
Kang X;Zhou M;Wang S;Jin S;Sun G;Zhu M;Jin R
在原子水平上定制纳米团簇导致四面体形状的FCC Pt 1Ag 28（S-Adm）18（PPh 3）4纳米团簇和光致发光的大增强。合金纳米团簇（NC）的原子结构表征仍然具有挑战性，但对于理解协同作用和基于合金NC的独特性质开发新应用至关重要。本文报道了具有四面体结构的Pt 1Ag 28（S-Adm）18（PPh 3）4纳米团簇的合成和X射线晶体结构。Pt 1Ag 28是通过Pt 1Ag 24（SPhMe 2）18同时与Adm-SH（1-金刚烷乙氧基化物）和PPh 3配体反应合成的。在Pt 1Ag 28 NC的金属框架和整体表面壳（Ag 16 S18 P4）中发现四面体结构，以及离散的Ag 4S 6P 1基序。Pt 1Ag 12内核采用面心立方（FCC）的安排，这是第一次在合金纳米团簇中观察到的同金和同银纳米粒子的二十面体结构的对比。Pt 1Ag 28纳米团簇表现出大大增强的光致发光（量子产率QY = 4.9%，发射中心在λ 672 nm），而起始材料（Pt 1Ag 24 NC）仅弱发光（QY = 0.1%）。通过电子动力学分析，获得了近50倍的发光增强。这项研究表明，通过控制结构的合金纳米团簇性能的原子级剪裁。
Tailoring the nanocluster at an atomic level leads to a tetrahedron-shaped FCC Pt1Ag28(S-Adm)18(PPh3)4 nanocluster and a large enhancement in photoluminescence. The atomic-structure characterization of alloy nanoclusters (NCs) remains challenging but is crucial in order to understand the synergism and develop new applications based upon the distinct properties of alloy NCs. Herein, we report the synthesis and X-ray crystal structure of the Pt1Ag28(S-Adm)18(PPh3)4 nanocluster with a tetrahedral shape. Pt1Ag28 was synthesized by reacting Pt1Ag24(SPhMe2)18 simultaneously with Adm-SH (1-adamantanethiol) and PPh3 ligands. A tetrahedral structure is found in the metal framework of Pt1Ag28 NC and an overall surface shell (Ag16S18P4), as well as discrete Ag4S6P1 motifs. The Pt1Ag12 kernel adopts a face-centered cubic (FCC) arrangement, which is observed for the first time in alloy nanoclusters in contrast to the commonly observed icosahedral structure of homogold and homosilver NCs. The Pt1Ag28 nanocluster exhibits largely enhanced photoluminescence (quantum yield QY = 4.9%, emission centered at ∼672 nm), whereas the starting material (Pt1Ag24 NC) is only weakly luminescent (QY = 0.1%). Insights into the nearly 50-fold enhancement of luminescence were obtained via the analysis of electronic dynamics. This study demonstrates the atomic-level tailoring of the alloy nanocluster properties by controlling the structure.