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.
|Journal||Chemistry - An Asian Journal|
|Publication status||Published - 2022 Jan 17|
Bibliographical noteFunding Information:
This work was supported by the National Research Foundation of Korea Grant funded by the Korean Government (NRF‐2018R1D1A1B07051018).
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All Science Journal Classification (ASJC) codes
- Organic Chemistry