Chemical and Electrochemical Behaviours of a New Phenolato‐Bridged Complex [(L)Mn^IIMn^II(L)]²⁺. Pathways to Mononuclear Chlorido [(L)Mn^II/III/IVCl]^0/1/2+ and Dinuclear Mono‐µ‐Oxido [(L)Mn^III(µ‐O)Mn^III/IV(L)]^2+/3+ Species

Abstract

The X-ray structure of a new dinuclear phenolato-bridged

An unusual two-dimensional 2-fold interpenetrating metal-organic framework based on tetranuclear manganese(II) clusters: Synthesis, structure and magnetic properties

“…The g parameter presents a value very close to 2.0, in accord with the presence of Mn(II) ions which do not exhibit spin-orbit coupling [30][31][32][33]. The obtained J values are in agreement with qualitative magnetostructural correlations found in Mn(II) complexes [34].…”

Activation of a water molecule using a mononuclear Mn complex: from Mn-aquo, to Mn-hydroxo, to Mn-oxyl via charge compensation

“…The latter band is tentatively attributed to a phenolate to manganese LMCT transition. 45–47,55,65 No transition was observed in the region around 1000 nm, thus discarding the possibility that a phenoxyl radical species is formed during oxidation. 35,66 …”

“…Similar bands have been reported in the literature for mononuclear Mn(III) 55,56 or dinuclear Mn(III)Mn(III) complexes. 46,47 The intense band at 380 nm is attributed to a phenolato to Mn(III) charge transfer transition. 55,57–59 According to the literature, the less intense band at 700 nm can plausibly be attributed to d-d transitions of 5 E → 5 T 2 parentage.…”

“…39–44 Appropriate modification of the charge of the ligand and atom donor set allows us to selectively form mononuclear 45–47 or mono-μ-oxo bridged dinuclear complexes. 47,48 More specifically we have previously reported on the formation of a dinuclear mono-μ-oxo bridged Mn(III)Mn(IV) complex by electrochemical oxidation of a mononuclear Mn(II) complex using a pentadentate [N 4 O] ligand (HL e in Scheme 1). 48 …”

Two New Supramolecular Architectures of Singly Phenoxo‐Bridged Copper(II) and Doubly Phenoxo‐Bridged Manganese(II) Complexes Derived from an Unusual ONOO Donor Hydrazone Ligand: Syntheses, Structural Variations, Cryomagnetic, DFT, and EPR Studies

“…The Mn–O bond lengths in Mn 2 O 2 core ranges from 2.172(3) Å to 2.222(3) Å. The average Mn–O–Mn bridge angle is slightly greater than that of the dinuclear phenolato‐bridged octahedral manganese(II) complexes derived from phenol containing ligand with NNNNO donor sets: 104.54° vs. 103.7° 12b. In 2 each manganese(II) center is surrounded by seven atoms: one (imine) nitrogen atom belonging to one [ L ] – ligand; one N 3 – ligand; five oxygen atoms [one (keto) oxygen atom, two (bridging phenoxo) oxygen atoms belonging to two [ L ] – , one (methoxy) oxygen atom belonging to the other unit of [ L ] – coordinated to the adjacent manganese center and one from the solvent molecule (MeOH in case of Mn1 and H 2 O for Mn2)].…”