Synthesis and structural characterization of inverse-coordination clusters from a two-electron superatomic copper nanocluster.
Synthesis and structural characterization of inverse-coordination clusters from a two-electron superatomic copper nanocluster.
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DOI：
10.1039/c8sc01508b
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发表时间：
2018-09-07
期刊：
影响因子：
8.4
通讯作者：
Liu CW
中科院分区：
文献类型：
--
作者：
Chakrahari KK;Silalahi RPB;Liao JH;Kahlal S;Liu YC;Lee JF;Chiang MH;Saillard JY;Liu CW
合成并表征了以十二配位主族元素（Cl，Br，S）为中心的立方八面体铜簇合物。合成了一系列立方八面体铜原子簇[Cu_（13）{S_2CNR_2}_6{CCR′}_4]（PF_6），1a-d（式中a：R = nBu，R′ = CO_2Me; B：R = nBu，R′ = CO_2Et; c：R = iPr，R′ = CO_2Et; d：R = nPr，R′ = 3，5-（CF_3）_2C_6H_3）; [Cu_（12）（μ_（12-S）{S_2CNR_2}6{CCR′}_4]，2a-c;[Cu12（μ12-Cl）{S2CNR2}6{CCR′}4]（PF 6），3a-e（其中e：R = nBu，R′ = Ph）; [Cu12（μ12-Br）{S2CNnBu2}6{CCPh}4]（PF 6），4e;和[Cu12（μ12-Cl）（μ3-Cl）{S2CNnBu2}6{CCCO2Me}3]+5a。簇1a是第一个结构特征的铜簇，具有Cu 13为中心的立方八面体排列，是块状铜fcc结构的缩影。此外，XANES证实了双电子超原子1中的部分Cu（0）特征。反配位团簇2-5是含有超配位数为12的主族元素（Cl、Br、S）的铜团簇的第一个例子。进行了理论和实验相结合的研究，这表明纳米团簇1中的中心铜（形式上为Cu 1-）可以被硫族元素/卤素原子取代，导致形成团簇2-5，其显示出增强的发光性质和主体-客体相互作用的离子分量的增加，如Br> Cl > S > Cu，这与Cu-X Wiberg指数一致。新化合物经ESI-MS、1H、13 C NMR、IR、UV-vis、发射光谱等表征，并经X-射线衍射分析确定其结构为2a-b、3d-e、4 e和5a。
Cuboctahedral copper clusters containing a twelve-coordinated main group element (Cl, Br, S) at the center have been synthesized and characterized. We have synthesized and structurally characterized a series of centred cuboctahedral copper clusters, namely [Cu13{S2CNR2}6{CCR′}4](PF6), 1a–d (where a: R = nBu, R′ = CO2Me; b: R = nBu, R′ = CO2Et; c: R = iPr, R′ = CO2Et; d: R = nPr, R′ = 3,5-(CF3)2C6H3); [Cu12(μ12-S){S2CNR2}6{CCR′}4], 2a–c; [Cu12(μ12-Cl){S2CNR2}6{CCR′}4](PF6), 3a–e (where e: R = nBu, R′ = Ph); [Cu12(μ12-Br){S2CNnBu2}6{CCPh}4](PF6), 4e; and [Cu12(μ12-Cl)(μ3-Cl){S2CNnBu2}6{CCCO2Me}3]+5a. Cluster 1a is the first structurally characterized copper cluster having a Cu13 centered cuboctahedral arrangement, a miniature of the bulk copper fcc structure. Furthermore, the partial Cu(0) character in the 2-electron superatoms 1 was confirmed by XANES. Inverse coordination clusters 2–5 are the first examples of copper clusters containing main group elements (Cl, Br, S) with a hyper-coordination number, twelve. A combined theoretical and experimental study was performed, which shows that the central copper (formally Cu1–) in nanoclusters 1 can be replaced by chalcogen/halogen atoms, resulting in the formation of clusters 2–5 which show enhanced luminescence properties and increase in the ionic component of the host–guest interaction as Br ≈ Cl > S > Cu, which is consistent with the Cu–X Wiberg indices. The new compounds have been characterized by ESI-MS, 1H, 13C NMR, IR, UV-visible, emission spectroscopy, and the structures 2a–b, 3d–e, 4e and 5a were established by X-ray diffraction analysis.
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