A new photoactivable NO-releasing {Ru−NO}6 ruthenium nitrosyl complex with a tetradentate ligand containing aniline and pyridine moieties

Jang Hoon Cho, Minyoung Kim, Youngmin You, Hong In Lee

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Abstract

A new type of photoactivable NO-releasing ruthenium nitrosyl complex, [Ru(EPBP)Cl(NO)], with a tetradentate ligand, N,N’-(ethane-1,2-diyldi-o-phenylene)-bis(pyridine-2-carboxamide) (= H2EPBP) was synthesized. Single crystal X-ray crystallography revealed that the complex has a distorted octahedral coordination geometry and NO is positioned at cis to Cl ion. NO-photolysis was observed under a white room light. The photodissociation of Ru−NO bond was identified by various techniques including X-ray crystallography, IR, UV/Vis absorption, electron paramagnetic resonance (EPR), and NMR spectroscopies. Quantum yields for the NO-photolysis of the complex in CH3OH, CHCl3, DMSO, CH3CN, and CH3NO2 were measured to be 0.19–0.36 with 400 (±5) nm excitation. Density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations were performed to understand the details of the photodissociation of the complex. The calculations suggest that the NO photolysis is most likely initiated by the electronic transition from the aniline moiety π MOs (π (aniline)) of the EPBP2− chelating ligand to the π-antibonding MO of Ru−NO (π*(Ru−NO)). Experimental and theoretical investigations indicate that the EPBP2− ligand provides an effective platform forming ruthenium nitrosyl complexes useful for NO-photoreleasing.

Original languageEnglish
Article numbere202101244
JournalChemistry - An Asian Journal
Volume17
Issue number2
DOIs
StatePublished - 17 Jan 2022

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