Density functional theory studies on a designed photoactive {FeNO}(6) nitrosyl and the corresponding photoinactive {FeNO}(7) species: Insight into the origin of NO photolability

作者：Fry Nicole L; Zhao Xiao P; Mascharak Pradip K^*

来源：Inorganica Chimica Acta, 2011, 367(1): 194-198.

DOI：10.1016/j.ica.2010.12.041

• Photoactive
• Iron nitrosyls
• DFT
• TDDFT
• NO photolability

Density functional theory (DFT) and time-dependent DFT (TDDFT) studies on a photoactive {FeNO}(6) nitrosyl [(PaPy3)Fe(NO)](ClO4)(2) (1) and the corresponding light-insensitive {FeNO}(7) species [(PaPy3) Fe (NO)](ClO4) (2) have been carried out to determine the origin of NO photolability of 1. The iron center in these two nitrosyls formally exists in 2+ oxidation state and the difference in pi-accepting ability of NO+ in 1 versus NO center dot in 2 greatly affects the extent of NO photolability of these two nitrosyls. Low energy transitions from the carboxamido/pi(FeNO) to the FeNO antibonding molecular orbitals lead to release of NO from 1 upon exposure to visible light. The decreased pi-accepting ability of the NO center dot moiety in 2 does not favor such transitions; instead transitions from orbitals centered at the FeNO unit to the pi(py) orbitals of the ligand frame become more favorable and the photolability of NO is lost in 2.

• 出版日期2011-2-28