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Selective and High‐Yield Synthesis of Oblate Superatom [PdAu 8 (PPh 3 ) 8 ] 2+
Author(s) -
Matsuo Shota,
Takano Shinjiro,
Yamazoe Seiji,
Koyasu Kiichirou,
Tsukuda Tatsuya
Publication year - 2016
Publication title -
chemelectrochem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.182
H-Index - 59
ISSN - 2196-0216
DOI - 10.1002/celc.201600115
Subject(s) - homo/lumo , superatom , chemistry , crystallography , molecular orbital , atomic orbital , atom (system on chip) , yield (engineering) , oblate spheroid , density functional theory , atomic physics , materials science , computational chemistry , physics , electron , molecule , organic chemistry , quantum mechanics , computer science , metallurgy , embedded system
We report herein a selective and high‐yield synthesis of [PdAu 8 (PPh 3 ) 8 ]Cl 2 through kinetic control over the co‐reduction of AuCl(PPh 3 ) and Pd(PPh 3 ) 4 and post‐synthesis annealing. Single‐crystal X‐ray diffraction confirmed that the PdAu 8 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 1.66 eV by using electrochemical measurements. Density functional theory calculations showed that both the HOMO and LUMO are assigned to 1P superatomic orbitals, and that the PdAu 8 2+ core can be viewed as an oblate superatom with an electronic configuration of (1S) 2 (1P) 4 . The optical gap (1.95 eV) was larger than the electrochemical HOMO–LUMO energy gap, because electronic transition from the HOMO to the LUMO is optically forbidden.