In order to examine the role(s) of designed ligands on the NO photolability of {Ru-NO}(6) nitrosyls, a set of three nitrosyls with ligands containing two carboxamide groups along with a varying number of phenolates have been synthesized. The nitrosyls namely, (NEt(4))(2)[(hybeb)Ru(NO)(OEt)] (1), (PPh(4))[(hypyb)Ru(NO)(OEt)] (2), and [(bpb)Ru(NO)(OEt)] (3) have been characterized by X-ray crystallography. Complexes 1-3 are diamagnetic, exhibit nu(NO) in the range 1780-1840 cm(-1) and rapidly release NO in solution upon exposure to low power UV light (7 mW/cm(2)). Density Functional Theory (DFT) and Time Dependent DFT (TDDFT) calculations on 1-3 indicate considerable contribution of ligand orbitals in the MOs involved in transitions leading to NO photolability. The results of the theoretical studies match well with the experimental absorption spectra as well as the parameters for NO photorelease and provide insight into the transition(s) associated with loss of NO.
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| http://dx.doi.org/10.1021/ic9017129 | DOI Listing |
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