ABSTRACT
In this study, we introduced the electron-donating group (-OH) to the aromatic rings of Ru(salophen)(NO)Cl (0) (salophenH2 =N,N'-(1,2-phenylene)bis(salicylideneimine)) to investigate the influence of the substitution on NO photolysis and NO-releasing dynamics. Three derivative complexes, Ru((o-OH)2 -salophen)(NO)Cl (1), Ru((m-OH)2 -salophen)(NO)Cl (2), and Ru((p-OH)2 -salophen)(NO)Cl (3) were developed and their NO photolysis was monitored by using UV/Vis, EPR, NMR, and IR spectroscopies under white room light. Spectroscopic results indicated that the complexes were diamagnetic Ru(II)-NO+ species which were converted to low-spin Ru(III) species (d5 , S=1/2) and released NO radicals by photons. The conversion was also confirmed by determining the single-crystal structure of the photoproduct of 1. The photochemical quantum yields (ΦNO s) of the photolysis were determined to be 0>1, 2, 3 at both the visible and UV excitations. Femtosecond (fs) time-resolved mid-IR spectroscopy was employed for studying NO-releasing dynamics. The geminate rebinding (GR) rates of the photoreleased NO to the photolyzed complexes were estimated to be 0≃1, 2, 3. DFT and TDDFT computations found that the introduction of the hydroxyl groups elevated the ligand π-bonding orbitals (π (salophen)), resulting in decrease of the HOMO-LUMO gaps in 1-3. The theoretical calculations suggested that the Ru-NNO bond dissociations of the complexes were mostly initiated by the ligand-to-ligand charge transfer (LLCT) of π(salophen)âπ*(Ru-NO) with both the visible and UV excitations and the decreasing ΦNO s could be explained by the changes of the electronic structures in which the photoactivable bands of 1-3 have relatively less contribution of transitions related with Ru-NO bond than those of 0.
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) (= H2 EPBP) 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 CH3 OH, CHCl3 , DMSO, CH3 CN, and CH3 NO2 were measured to be 0.19-0.36 with 400 (±5)â 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.