Metal Oxo-Fluoride Molecules OnMF2 (M = Mn and Fe; n=1-4) and O2MnF: Matrix Infrared Spectra and Quantum Chemistry

Huang, Tengfei1; Zhao, Lijuan2,3; Jiang, Xuelian4; Yu, Wenjie1; Xu, Bing1; Wang, Xuefeng1; Schwarz, W. H. Eugen2,3,5; Li, Jun2,3,4

2021-06-07

10.1021/acs.inorgchem.0c03806

INORGANIC CHEMISTRY   影响因子和分区

0020-1669

1520-510X

On reacting laser-ablated manganese or iron difluorides with O-2 or O-3 during codeposition in solid neon or argon, infrared absorptions of several new metal oxofluoride molecules, including OMF2, (eta(1)-O-2 )MF2, (eta(2)-O-3)MF2, (eta(1)-O-2)(2)MF2 (M = Mn and Fe), and O2MnF, have been observed. Quantum chemical density functional and multiconfiguration wavefunction calculations have been applied to characterize these new products by their geometric and electronic structures, vibrations, charges, and bonding. The assignment of the main vibrational absorptions as dominant symmetric or antisymmetric M-F or M-O stretching modes is confirmed by oxygen isotopic shifts and quantum chemical calculations of frequencies and thermal stabilities. The tendency of Fe to form polyoxygen complexes in lower oxidation states than the preceding element Mn is affirmed experimentally and supported theoretically. The M-F stretching frequencies of the isolated metal oxo-fluorides may provide a scale for the local charge on the MF2 sites in active energy conversion systems. The study of these species provides insights for understanding the trend of oxidation state changes across the transition-metal series.

SCI ; EI

英语

NI论文

通讯

National Natural Science Foundation of China[21873070,22033005] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002]

Chemistry

Chemistry, Inorganic & Nuclear

WOS:000661306200014

AMER CHEMICAL SOC

20212510528178

Argon lasers ; Chemical bonds ; Electronic structure ; Energy conversion ; Fluorine compounds ; Iron compounds ; Light absorption ; Molecules ; Quantum chemistry ; Transition metals

Energy Conversion Issues:525.5 ; Metallurgy and Metallography:531 ; Light/Optics:741.1 ; Lasers, General:744.1 ; Physical Chemistry:801.4 ; Atomic and Molecular Physics:931.3

CHEMISTRY

Web of Science

1.Tongji Univ, Sch Chem Sci & Engn, Shanghai 200092, Peoples R China
2.Tsinghua Univ, Dept Chem, Beijing 100084, Peoples R China
3.Tsinghua Univ, Minist Educ, Key Lab Organ Optoelect & Mol Engn, Beijing 100084, Peoples R China
4.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China
5.Siegen Univ, Dept Chem, D-57068 Siegen, Germany

Huang, Tengfei,Zhao, Lijuan,Jiang, Xuelian,et al. Metal Oxo-Fluoride Molecules OnMF2 (M = Mn and Fe; n=1-4) and O2MnF: Matrix Infrared Spectra and Quantum Chemistry[J]. INORGANIC CHEMISTRY,2021,60(11):7687-7696.

Huang, Tengfei.,Zhao, Lijuan.,Jiang, Xuelian.,Yu, Wenjie.,Xu, Bing.,...&Li, Jun.(2021).Metal Oxo-Fluoride Molecules OnMF2 (M = Mn and Fe; n=1-4) and O2MnF: Matrix Infrared Spectra and Quantum Chemistry.INORGANIC CHEMISTRY,60(11),7687-7696.

Huang, Tengfei,et al."Metal Oxo-Fluoride Molecules OnMF2 (M = Mn and Fe; n=1-4) and O2MnF: Matrix Infrared Spectra and Quantum Chemistry".INORGANIC CHEMISTRY 60.11(2021):7687-7696.