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Title: Probing the electronic structure of [Ru(L1)2]: Z(z = 0, 1+ and 2+) (H2L1: A tridentate 2-aminophenol derivative) complexes in three ligand redox levels
Authors: Saha A.
Rajput A.
Gupta, Puneet
Mukherjee R.
Published in: Dalton Transactions
Abstract: Aerobic reaction between [RuII(DMSO)4Cl2], a redox-active 2-aminophenol-based ligand (H2L1: 2-[2-(benzylthio)phenylamino]-4,6-di-tert-butylphenol) and Et3N in MeOH under refluxing conditions afforded a purple complex [Ru(L1)2] (S = 0). Structural analysis reveals that the tridentate ligand coordinates in a mer conformation providing a distorted octahedral RuN2O2S2 coordination. Cyclic voltammetry on 1 in CH2Cl2 reveals the accessability of the monocation, dication and monoanion forms. Reddish purple monocation [Ru(L1)2](PF6)·CH2Cl2 ([1OX1](PF6)·CH2Cl2; S = 1/2) and green dication [Ru(L1)2](BF4)2·H2O ([1OX2](BF4)2·H2O; S = 0) have been isolated through the chemical oxidation of 1 in CH2Cl2 by [FeIII(η5-C5H5)2](PF6) and AgBF4, respectively. A structural analysis of the single crystals of the monocation and the dication with the compositions [1OX1](PF6)·CH2Cl2·H2O (2) and [1OX2](BF4)2·1.7H2O (3), respectively, has been done. Metrical (metal-ligand and ligand backbone) parameters, values of metrical oxidation states of coordinated ligands, 1H NMR spectra of 1 and [1OX2](BF4)2·H2O, EPR spectra of [1OX1](PF6)·CH2Cl2, X-ray photoelectron and UV-VIS-NIR spectra of 1-3, spin population analysis from broken-symmetry (BS) density functional theory (DFT) calculations and quasi-restricted orbital (QRO) analysis have allowed us to assign the electronic structure of the complexes. The complexes exhibit highly covalent metal-ligand interactions. The electronic states of 1, [1OX1]1+ and [1OX2]2+ are best described as [RuII{(LISQ)-}2] ↔ [RuIII{(LAP)2-}{(LISQ)-}] (S = 0), [RuIII{(LISQ)-}2]1+ (S = 1/2) and [RuII{(LIBQ)0}2]2+ ↔ [RuIII{(LISQ)-}{(LIBQ)0}]2+ (S = 0), respectively. Notably, all redox processes are ligand-centred. Absorption spectral properties have been rationalized based on time-dependent (TD)-DFT calculations. For 1, the appearance of an IVCT band at 1100 nm supports its Class II-III (borderline) ligand-based mixed-valence character. © 2020 The Royal Society of Chemistry.
Citation: Dalton Transactions, 49(43): 15355-15375
Issue Date: 2020
Publisher: Royal Society of Chemistry
Keywords: Complexation
Cyclic voltammetry
Density functional theory
Dimethyl sulfoxide
Electron spin resonance spectroscopy
Electronic states
Electronic structure
Iron compounds
Metal analysis
Nuclear magnetic resonance spectroscopy
Photoelectron spectroscopy
Redox reactions
Structural analysis
Ultraviolet spectroscopy
Chemical oxidation
Coordinated ligands
Ligand-based mixed valence
Metal-ligand interactions
Refluxing condition
Spectral properties
UV-VIS-NIR spectra
X-ray photoelectrons
Ruthenium compounds
ISSN: 14779226
Author Scopus IDs: 57194548522
Author Affiliations: Saha, A., Department of Chemical Sciences, Indian Institute of Science Education and Research, Kolkata, Mohanpur, 741 246, India
Rajput, A., Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, 208 016, India, Department of Chemistry, School of Basic and Applied Sciences, G. D. Goenka University, Sohna Road, Gurugram, Haryana, 122 103, India
Gupta, P., Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee, 247 667, India
Mukherjee, R., Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, 208 016, India
Funding Details: Financial assistance (CRG/2018/000151) received from the Science and Engineering Research Board (SERB), Department of Science & Technology, Government of India, is gratefully acknowledged. Financial support received from the Department of Chemical Sciences, IISER Kolkata, is highly appreciated. AS acknowledges Dr Suman Kumar Barman of IIT Kanpur for his help in many ways. AS sincerely acknowledges Dr Suvendu Maity for his help in recording the EPR spectra at Ramakrishna Mission Residential College, Narendrapur, Kolkata. AS gratefully acknowledges the award of SRF by the Council of Scientific & Industrial Research, Government of India. PG acknowledges IIT Roorkee for the Faculty Initiation Grant (FIG-100810) and computational facilities for running ORCA codes to perform QRO analysis. Department of Science and Technology, Ministry of Science and Technology, India, डीएसटी; Science and Engineering Research Board, SERB
Corresponding Author: Mukherjee, R.; Department of Chemistry, India; email:
Appears in Collections:Journal Publications [CY]

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