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Photosensitive Tin Sulfur Dioxide Complexes with Unexpected Bonding Modes
Author(s) -
Liu Xing,
Liu XiaoRui
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201806154
Subject(s) - isomerization , chemistry , tin , molecule , molecular vibration , infrared spectroscopy , photochemistry , atom (system on chip) , crystallography , annealing (glass) , infrared , materials science , catalysis , organic chemistry , computer science , composite material , embedded system , physics , optics
Infrared spectra of the matrix‐isolated Sn( η 2 ‐O 2 S), Sn( η 2 ‐OSO), Sn( η 2 ‐O 2 S)( η 1 ‐OSO), Sn( η 2 ‐O 2 S) 2, OSn 2 ( η 2 ‐SO), and Sn( μ 2 ‐O 2 )SnS molecules were observed following laser‐ablated Sn atom reactions with SO 2 during condensation in solid argon. The assignments for the major vibrational modes were confirmed by appropriate S 18 O 2 and 34 SO 2 isotopic shifts and density functional vibrational frequency calculations (B3LYP and BPW91). Interestingly, the mononuclear complexes are interconvertible; that is, irradiation induces the isomerization of Sn( η 2 ‐O 2 S) and Sn( η 2 ‐O 2 S)( η 1 ‐OSO) to Sn( η 2 ‐OSO) and Sn( η 2 ‐O 2 S) 2 , respectively, and vice versa on annealing. However, there is no evidence of isomerization reaction in between the binuclear molecules OSn 2 ( η 2 ‐SO) and Sn( μ 2 ‐O 2 )SnS. Bonding in these products is discussed, and the electronic structure changes associated with different bonding types are revealed, which is crucial for the observed photochemical reactions.