Selective and High-Yield Synthesis of Oblate Superatom [PdAu8(PPh3)8]2+
Selective and High-Yield Synthesis of Oblate Superatom [PdAu8(PPh3)8]2+
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DOI：
10.1002/celc.201600115
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发表时间：
2016-08-01
期刊：
影响因子：
4
通讯作者：
Tsukuda, Tatsuya
中科院分区：
文献类型：
--
作者：
Matsuo, Shota;Takano, Shinjiro;Tsukuda, Tatsuya
本文报道了通过动力学控制AuCl（PPh3）和Pd（PPh3）（4）的共还原和合成后退火来选择性和高产率地合成[PdAu8（PPh3）（8）] Cl-2。单晶X射线衍射证实，PdAu8核心具有中心冠基序，Pd原子位于中心。通过电化学测量确定了最高占据分子轨道（HOMO）和最低未占据分子轨道（LUMO）之间的能隙为1.66eV。密度泛函理论计算表明，HOMO和LUMO都归属于1P超原子轨道，PdAu 82+核可以看作是一个扁扁超原子，电子组态为（1S）（2）（1P）（4）.光学带隙（1.95eV）大于电化学HOMO-LUMO能隙，因为从HOMO到LUMO的电子跃迁是光学禁止的。
We report herein a selective and high-yield synthesis of [PdAu8(PPh3)(8)]Cl-2 through kinetic control over the co-reduction of AuCl(PPh3) and Pd(PPh3)(4) and post-synthesis annealing. Single-crystal X-ray diffraction confirmed that the PdAu8 core has a centered-crown motif with the Pd atom located at the center. The energy gap between the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) was determined to be 1.66eV by using electrochemical measurements. Density functional theory calculations showed that both the HOMO and LUMO are assigned to 1P superatomic orbitals, and that the PdAu82+ core can be viewed as an oblate superatom with an electronic configuration of (1S)(2)(1P)(4). The optical gap (1.95eV) was larger than the electrochemical HOMO-LUMO energy gap, because electronic transition from the HOMO to the LUMO is optically forbidden.