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Synthesis and structural characterization of inverse-coordination clusters from a two-electron superatomic copper nanocluster†
Chemical Science ( IF 8.4 ) Pub Date : 2018-07-02 00:00:00 , DOI: 10.1039/c8sc01508b Kiran Kumarvarma Chakrahari,Rhone P. Brocha Silalahi,Jian-Hong Liao,Samia Kahlal,Yu-Chiao Liu,Jyh-Fu Lee,Ming-Hsi Chiang,Jean-Yves Saillard,C. W. Liu
Chemical Science ( IF 8.4 ) Pub Date : 2018-07-02 00:00:00 , DOI: 10.1039/c8sc01508b Kiran Kumarvarma Chakrahari,Rhone P. Brocha Silalahi,Jian-Hong Liao,Samia Kahlal,Yu-Chiao Liu,Jyh-Fu Lee,Ming-Hsi Chiang,Jean-Yves Saillard,C. W. Liu
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We have synthesized and structurally characterized a series of centred cuboctahedral copper clusters, namely [Cu13{S2CNR2}6{C![[triple bond, length as m-dash]](https://www.rsc.org/images/entities/char_e002.gif)
CR′}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.
中文翻译：
双电子超原子铜纳米团簇反配位团簇的合成和结构表征†
我们合成并表征了一系列中心立方八面体铜簇，即 [Cu 13 {S 2 CNR 2 } 6 {CCR′} 4 ](PF 6 ), 1a–d（其中a : R = n Bu, R ′ = CO 2 Me；b：R = n Bu，R′ = CO 2 Et；c：R = i Pr，R′ = CO 2 Et；d：R = n Pr，R′ = 3,5-(CF 3 ) 2C 6 H 3 ) ; [Cu 12 (μ 12 -S){S 2 CNR 2 } 6 {C CR′} 4 ], 2a–c ; [Cu 12 (μ 12 -Cl){S 2 CNR 2 } 6 {C CR′} 4 ](PF 6 ), 3a–e（其中e : R = n Bu, R′ = Ph）；[Cu 12 (μ 12 -Br){S 2 CN n Bu 2 } 6 {C CPh} 4 ](PF 6 ), 4e；[Cu 12 (μ 12 -Cl)(μ 3 -Cl){S 2 CN n Bu 2 } 6 {C CCO 2 Me} 3 ] + 5a。簇1a是第一个结构特征铜簇，具有以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2电子超原子1中的部分Cu(0)特征。逆配位簇2-5是含有主族元素（Cl、Br、S）的铜簇的第一个例子，超配位数为 12。综合理论和实验研究表明，纳米团簇1中的中心铜（以前称为 Cu 1−）可以被硫族/卤素原子取代，从而形成团簇2-5其显示出增强的发光性能和主客体相互作用的离子成分的增加，即 Br ≈ Cl > S > Cu，这与 Cu-X Wiberg 指数一致。新化合物通过ESI-MS、 1 H、13 C NMR、IR、UV-visible、发射光谱进行表征，并通过X射线衍射分析确定了结构2a–b、3d–e、4e和5a 。
更新日期：2018-07-02
CR′}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.
中文翻译：
双电子超原子铜纳米团簇反配位团簇的合成和结构表征†
我们合成并表征了一系列中心立方八面体铜簇，即 [Cu 13 {S 2 CNR 2 } 6 {C
CR′} 4 ](PF 6 ), 1a–d（其中a : R = n Bu, R ′ = CO 2 Me；b：R = n Bu，R′ = CO 2 Et；c：R = i Pr，R′ = CO 2 Et；d：R = n Pr，R′ = 3,5-(CF 3 ) 2C 6 H 3 ) ; [Cu 12 (μ 12 -S){S 2 CNR 2 } 6 {C CR′} 4 ], 2a–c ; [Cu 12 (μ 12 -Cl){S 2 CNR 2 } 6 {C CR′} 4 ](PF 6 ), 3a–e（其中e : R = n Bu, R′ = Ph）；[Cu 12 (μ 12 -Br){S 2 CN n Bu 2 } 6 {C CPh} 4 ](PF 6 ), 4e；[Cu 12 (μ 12 -Cl)(μ 3 -Cl){S 2 CN n Bu 2 } 6 {C CCO 2 Me} 3 ] + 5a。簇1a是第一个结构特征铜簇，具有以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2电子超原子1中的部分Cu(0)特征。逆配位簇2-5是含有主族元素（Cl、Br、S）的铜簇的第一个例子，超配位数为 12。综合理论和实验研究表明，纳米团簇1中的中心铜（以前称为 Cu 1−）可以被硫族/卤素原子取代，从而形成团簇2-5其显示出增强的发光性能和主客体相互作用的离子成分的增加，即 Br ≈ Cl > S > Cu，这与 Cu-X Wiberg 指数一致。新化合物通过ESI-MS、 1 H、13 C NMR、IR、UV-visible、发射光谱进行表征，并通过X射线衍射分析确定了结构2a–b、3d–e、4e和5a 。
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