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A DFT Study on the Electronic and Redox Properties of [PW 11 O 39 (ReN)] n – ( n = 3, 4, 5) and [PW 11 O 39 (OsN)] 2–
Author(s) -
Yan LiKai,
Dou Zhuo,
Guan Wei,
Shi ShaoQing,
Su ZhongMin
Publication year - 2006
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200600720
Subject(s) - chemistry , osmium , polyoxometalate , rhenium , redox , homo/lumo , transition metal , crystallography , electronic structure , inorganic chemistry , computational chemistry , catalysis , ruthenium , molecule , organic chemistry
DFT calculations were carried out to investigate the electronic and redox properties of nitrido‐functionalized polyoxometalate species, [PW 11 O 39 (ReN)] n – ( n = 3, 4, 5) and [PW 11 O 39 (OsN)] 2– . The rhenium‐ and osmium‐nitrido effectively modify the electronic properties. The LUMOs in fully oxidized [PW 11 O 39 (ReN)] 3– and [PW 11 O 39 (OsN)] 2– are mainly concentrated on the Re and Os centers. The high‐valent transition metals Re and Os modify the components and energies of the LUMO. The LUMO energies of [PW 11 O 39 (ReN)] 3– and [PW 11 O 39 (OsN)] 2– are lower than that of related Keggin [PW 12 O 40 ] 3– . In addition, Re centers will prefer to accept the electrons in the first and second reduced process of fully oxidized [PW 11 O 39 (ReN)] 3– . (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)