Iron(III) Complexes of a Hexadentate Thioether-Appended 2-Aminophenol Ligand: Redox-Driven Spin State Switchover

Akram Ali; Saumitra Bhowmik; Suman K Barman; Narottam Mukhopadhyay; Christine E Glüer Nee Schiewer; Francesc Lloret; Franc Meyer; Rabindranath Mukherjee

doi:10.1021/acs.inorgchem.1c03992

Iron(III) Complexes of a Hexadentate Thioether-Appended 2-Aminophenol Ligand: Redox-Driven Spin State Switchover

Inorg Chem. 2022 Apr 4;61(13):5292-5308. doi: 10.1021/acs.inorgchem.1c03992. Epub 2022 Mar 21.

Authors

Akram Ali¹, Saumitra Bhowmik², Suman K Barman¹, Narottam Mukhopadhyay², Christine E Glüer Nee Schiewer³, Francesc Lloret⁴, Franc Meyer³, Rabindranath Mukherjee¹

Affiliations

¹ Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur 208016, India.
² Department of Chemical Sciences, Indian Institute of Science Education and Research Kolkata, Mohanpur, West Bengal 741246, India.
³ Institute of Inorganic Chemistry, University of Göttingen, Tammannstrasse 4, D-37077 Göttingen, Germany.
⁴ Departament de Quımíca, Inorgànica/Instituto de Ciencia Molecular (ICMOL), Universitat de Valeńcia, Polígono de la Coma, s/n, Paterna, València 46980, Spain.

PMID: 35312298
DOI: 10.1021/acs.inorgchem.1c03992

Abstract

A green complex [Fe(L³)] (1), supported by the deprotonated form of a hexadentate noninnocent redox-active thioether-appended 2-aminophenolate ligand (H₄L³ = N,N'-bis(2-hydroxy-3,5-di-tert-butylphenyl)-2,2'-diamino(diphenyldithio)ethane), has been synthesized and structurally characterized at 100(2) K and 298(2) K. In CH₂Cl₂, 1 displays two oxidative and a reductive one-electron redox processes at E_1/2 values of -0.52 and 0.20 V, and -0.85 V versus the Fc⁺/Fc redox couple, respectively. The one-electron oxidized 1⁺ and one-electron reduced 1^- forms, isolated as a blackish-blue solid 1(PF₆)·CH₂Cl₂ (2) and a gray solid [Co(η⁵-C₅H₅)₂]1·DMF (3), have been structurally characterized at 100(2) K. Structural parameters at 100 K of the ligand backbone and metrical oxidation state values unambiguously establish the electronic states as [Fe^III{(L^AP_O,N)^2-}{(L^ISQ_O,N)^•-}{(L_S,S)⁰}] (1) (two tridentate halves are electronically asymmetric-ligand mixed-valency), [Fe^III{(L^ISQ_O,N)^•-}{(L^ISQ_O,N)^•-}{(L_S,S)⁰}]⁺ (1⁺), and [Fe^III{(L^AP_O,N)^2-}{(L^AP_O,N)^2-}{(L_S,S)⁰}]^- (1^-) [dianionic 2-amidophenolate(2-) (L^AP_O,N)^2- and monoanionic 2-iminobenzosemiquinonate(1-) π-radical (S_rad = 1/2) (L^ISQ)^•- redox level]. Mössbauer spectral data of 1 at 295, 200, and 80 K reveal that it has a major low-spin (ls)-Fe(III) and a minor ls-Fe(II) component (redox isomers), and at 7 K, the major component exists exclusively. Thus, in 1, the occurrence of a thermally driven valence-tautomeric (VT) equilibrium (asymmetric) [Fe^III{(L^AP_O,N)^2-}{(L^ISQ_O,N)^•-}{(L_S,S)⁰}] ⇌ (symmetric) [Fe^II{(L^ISQ_O,N)^•-}{(L^ISQ_O,N)^•-}{(L_S,S)⁰}] (80-295 K) is implicated. Mössbauer spectral parameters unequivocally establish that 1⁺ is a ls-Fe(III) complex. In contrast, the monoanion 1^- contains a high-spin (hs)-Fe(III) center (S_Fe = 5/2), as is deduced from its Mössbauer and EPR spectra. Complexes 1-3 possess total spin ground states S_t = 0, 1/2, and 5/2, respectively, based on ¹H NMR and EPR spectra, the variable-temperature (2-300 K) magnetic behavior of 2, and the μ_eff value of 3 at 300 K. Broken-symmetry density functional theory (DFT) calculations at the B3LYP-level of theory reveal that the unpaired electron in 1⁺/2 is due to the (L^ISQ)^•- redox level [ls-Fe(III) (S_Fe = 1/2) is strongly antiferromagnetically coupled to one of the (L^ISQ)^•- radicals (S_rad = 1/2)], and 1^-/3 is a hs-Fe(III) complex, supported by (L³)^4- with two-halves in the (L^AP)^2- redox level. Complex 1 can have either a symmetric or asymmetric electronic state. As per DFT calculation, the former state is stabilized by -3.9 kcal/mol over the latter (DFT usually stabilizes electronically symmetric structure). Time-dependent (TD)-DFT calculations shed light on the origin of observed UV-vis-NIR spectral absorptions for 1-3 and corroborate the results of spectroelectrochemical experiments (300-1100 nm) on 1 (CH₂Cl₂; 298 K). Variable-temperature (218-298 K; CH₂Cl₂) absorption spectral (400-1000 nm) studies on 1 justify the presence of VT equilibrium in the solution-state.