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Issue 33, 2014
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Comparative photo-release of nitric oxide from isomers of substituted terpyridinenitrosylruthenium(ii) complexes: experimental and computational investigations

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Abstract

The 4′-(2-fluorenyl)-2,2′:6′,2′′-terpyridine (FT) ligand and its cis(Cl,Cl)- and trans(Cl,Cl)-[RuII(FT)Cl2(NO)](PF6) complexes have been synthesized. Both isomers were separated by HPLC and fully characterized by 1H and 13C NMR. The X-ray diffraction crystal structures were solved for FT (Pna21 space group, a = 34.960(4), b = 5.9306(7), c = 9.5911(10) Å), and trans(Cl,Cl)-[RuII(FT)Cl2(NO)](PF6)·MeOH (P[1 with combining macron] space group, a = 10.3340(5), b = 13.0961(6), c = 13.2279(6) Å, α = 72.680(2), β = 70.488(2), γ = 67.090(2)°). Photo-release of NO˙ radicals occurs under irradiation at 405 nm, with a quantum yield of 0.31 and 0.10 for cis(Cl,Cl)-[RuII(FT)Cl2(NO)](PF6) and trans(Cl,Cl)-[RuII(FT)Cl2(NO)](PF6), respectively. This significant difference is likely due to the trans effect of Cl, which favors the photo-release. UV-visible spectroscopy and cyclic voltammetry indicate the formation of ruthenium(III) species as photoproducts. A density functional theory (DFT) analysis provides a rationale for the understanding of the photo-physical properties, and allows relating the weakening of the Ru–NO bond, and finally the photo-dissociation, to HOMO → LUMO excitations.

Graphical abstract: Comparative photo-release of nitric oxide from isomers of substituted terpyridinenitrosylruthenium(ii) complexes: experimental and computational investigations

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Supplementary files

Article information


Submitted
02 Apr 2014
Accepted
24 Jun 2014
First published
24 Jun 2014

Dalton Trans., 2014,43, 12721-12733
Article type
Paper
Author version available

Comparative photo-release of nitric oxide from isomers of substituted terpyridinenitrosylruthenium(II) complexes: experimental and computational investigations

J. Akl, I. Sasaki, P. G. Lacroix, I. Malfant, S. Mallet-Ladeira, P. Vicendo, N. Farfán and R. Santillan, Dalton Trans., 2014, 43, 12721
DOI: 10.1039/C4DT00974F

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