Mn3 Single-Molecule Magnets and Mn6/Mn9 Clusters from the Use of Methyl 2-Pyridyl Ketone Oxime in Manganese Phosphinate and Phosphonate Chemistry

Adebayo, Olajuyigbe A.; Abboud, Khalil A.; Christou, George

doi:10.1021/acs.inorgchem.7b01793

Cited by 17 publications

(5 citation statements)

References 77 publications

(54 reference statements)

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“…The fitting of χ M of polynuclear magnetic compounds was a nontrivial issue, especially for manganese [ 39 ], in view of the overparameterization problem. We then decided to use an in-house software, based on full Hamiltonian diagonalization and Levenberg-Marquardt optimization, by first fitting χ M T data to the sum of two terms: ( i ) a Hamiltonian containing the isotropic exchange and Zeeman terms for the coupled dinuclear species, as reported in Equation (6), and ( ii ) the Zeeman term for the molar uncoupled fraction f [ 40 ], further augmented with a TIP component fixed at 600 × 10 −6 emu mol −1 , value typical for manganese(III) ions [ 41 ]. The best-fit parameters revealed to be relatively insensitive to the TIP value.…”

Section: Resultsmentioning

confidence: 99%

Selective Formation, Reactivity, Redox and Magnetic Properties of MnIII and FeIII Dinuclear Complexes with Shortened Salen-Type Schiff Base Ligands

Rigamonti

Zardi

Carlino

et al. 2020

IJMS

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The reactivity of the shortened salen-type ligands H3salmp, H2salmen and H2sal(p-X)ben with variable para-substituent on the central aromatic ring (X = tBu, Me, H, F, Cl, CF3, NO2) towards the trivalent metal ions manganese(III) and iron(III) is presented. The selective formation of the dinuclear complexes [M2(-salmp)2], M = Mn (1a), Fe (2a), [M2(-salmen)2(-OR)2)], R = Et, Me, H and M = Mn (3a–c) or Fe (4a–c), and (M2(-sal[p-X]ben)2(-OMe)2), X = tBu, Me, H, F, Cl, CF3, NO2 and M = Mn (5a–g) or Fe (6a–g), could be identified by reaction of the Schiff bases with metal salts and the base NEt3, and their characterization through elemental analysis, infrared spectroscopy, mass spectrometry and single-crystal X-ray diffraction of 2a2AcOEt, 2a2CH3CN and 3c2DMF was performed. In the case of iron(III) and H3salmp, when using NaOH as a base instead of NEt3, the dinuclear complexes [Fe2(-salmp)(-OR)(salim)2], R = Me, H (2b–c) could be isolated and spectroscopically characterized, including the crystal structure of 2b1.5H2O, which showed that rupture of one salmp3– to two coordinated salim– ligands and release of one salH molecule occurred. The same hydrolytic tendency could be identified with sal(p-X)ben ligands in the case of iron(III) also by using NEt3 or upon standing in solution, while manganese(III) did not promote such a C–N bond breakage. Cyclic voltammetry studies were performed for 3b, 4b, 5a and 6a, revealing that the iron(III) complexes can be irreversibly reduced to the mixed-valence FeIIFeIII and FeII2 dinuclear species, while the manganese(III) derivatives can be reversibly oxidized to either the mixed-valence MnIIIMnIV or to the MnIV2 dinuclear species. The super-exchange interaction between the metal centers, mediated by the bridging ligands, resulted in being antiferromagnetic (AFM) for the selected dinuclear compounds 3b, 4b, 5a, 5e, 5f, 6a and 6e. The coupling constants J (–2J Ŝ1·Ŝ2 formalism) had values around –13 cm–1 for manganese(III) compounds, among the largest AFM coupling constants reported so far for dinuclear MnIII2 derivatives, while values between –3 and –10 cm–1 were obtained for iron(III) compounds.

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Section: Resultsmentioning

confidence: 99%

Selective Formation, Reactivity, Redox and Magnetic Properties of MnIII and FeIII Dinuclear Complexes with Shortened Salen-Type Schiff Base Ligands

Rigamonti

Zardi

Carlino

et al. 2020

IJMS

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“…In a recent paper, Geng et al [166] showed that the magnetoelectric force microscopy (MeFM) that is a combination of magnetic force microscopy (MFM) with in situ modulated electric fields (E), can be employed to detect the E-induced magnetization (ME) and to show the multiferroic domain structure in hexagonal (h-)ErMnO 3 . Along with multiferroic materials (e.g., Cu 2 OSeO 3 ) [167], they exhibit the so-called magnetoelectric effect, in which an external magnetic field can cause electric polarization and an electric field can cause magnetic ordering. The field of the manipulation of magnetic structures by electrical fields is beyond the scope of this review, but it is highly desirable for technological applications.…”

Section: Magnetic Force Microscopy (Mfm)mentioning

confidence: 99%

“…The former [142][143][144][145][146][147][148][149][150][151][152][153][154][155] have led to a variety of clusters with exciting molecular structures and magnetic properties; they have been used, among others, in the development of a synthetic process widely known as "ground-state spin switching and enhancing SMM properties via targeted structural distortion" strategy [56,[142][143][144][145][147][148][149]. The latter [156][157][158][159][160][161][162][163][164][165][166][167][168][169][170][171][172][173][174], in addition to their involvement in the synthesis of 3d-metal SIMs [158], have provided access to interesting 3d-metal clusters and SMMs. They have also been used in the realization of a synthetic scheme best known as "'switching on' SMM properties upon conversion of low-spin complexes into high-spin ones without changing the core" strategy [168,169] and, when derivatized by design, in the development of an innovative approach which allows the covale...…”

Section: Molecular and Supramolecular Approaches In The Chemistry Of Manganese Smms Using Simple And Elaborate 2-pyridyl Oximesmentioning

confidence: 99%

Smart Tools for Smart Applications

2021

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She is currently working in the group of Professor E. Terreno at the molecular and preclinical imaging center in Turin as a member of the research team in the development and testing of innovative molecular imaging probes. Her interest is mainly focused on the visualization and monitoring of inflammatory processes using 1H and 19F magnetic resonance and optical and photoacoustic Imaging. Most of her research activities deal with the active targeting and tracking of the immune system cells in vivo, the visualization of the inflamed endothelium, and cell surveillance after transplantation using newly synthesized nano-and microsystems.Roberto Nisticò obtained his Ph.D. in Chemical and Materials Sciences at the University of Torino (Department of Chemistry, Italy). His research is focused on several aspects at the interface between nanotechnology and materials science, always looking for novel and appealing solutions for a sustainable future. His principal fields of interest are magnetic and/or metallic nanomaterials, functional/porous coatings, plasma treatments, biomaterials (for biomedical applications), valorization of natural resources, (bio)polymers and carbons, nanomaterials for photocatalysis, and AOPs. Federico Cesano received his Degree in Chemistry in 1999 at the University of Torino. After spending two years at the Italian National Research Council (2000-2002), he completed his Ph.D. in Material Science and Technology in 2005. Since 2006, he has been working at the Chemistry Dept. of the University of Turin. He is co-author of more than 70 papers and several book chapters published in the main journals of chemistry and materials science. His main research interests are 1D, 2D, and 3D nanostructured materials (including oxides, carbon nanomaterials, transition metal dichalcogenides, polymers), either alone or combined to form hybrid structures and composites. vii inorganics

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“…The rational design and synthesis of metal phosphinates has garnered great attention from many researchers relating to chemistry and materials science due to their application in various fields. − For instance, a cuboidal tetranuclear manganese constructed with diphenylphosphinic acid can act as an oxygen evolving complex for water oxidation in photosystem II . A cobalt compound built with a racemic phosphonate ligand can exhibit both polarity and ferromagnetism .…”

Section: Introductionmentioning

confidence: 99%

Various Silver Phosphinate Inorganic Architectures in Three-Dimensional Frameworks with Argentophilic Interactions

et al. 2019

Crystal Growth & Design

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Three silver compounds with the formulas: [Ag2(HL1)] (1), [Ag10(L2)2(H2O)1.25] (2), and [Ag5(L3)]·1.5H2O (3) were obtained by self-assembly of silver nitrate with 4,4′-phosphinicobis-dibenzoic acid (H3L1), 4,4′-phosphinicobis-diisophthalic acid (H5L2), and 2,2′-phosphinicobis-diisophthalic acid (H5L3) under hydrothermal conditions. The structures of these compounds were confirmed by various characterization methods. Both 1 and 2 crystallize in P21/n space group and present three-dimensional (3D) frameworks, which contain a sliver phosphinate inorganic chain or sheet formed by Ag–Ag interactions. Meanwhile, compound 3 is in C2/c space group and also displays a 3D silver-organic architecture. The open-framework contains narrow channels along the c-axis with an opening of 0.26 nm × 0.32 nm. The intriguing feature of the structure is emergence of a 3D inorganic skeleton in 3, which struts the whole framework. The 3D inorganic skeleton is generated from a silver phosphinite chain connected by strong Ag–Ag interactions. At room temperature, the compounds exhibit blue photoluminescence.

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Mn₃ Single-Molecule Magnets and Mn₆/Mn₉ Clusters from the Use of Methyl 2-Pyridyl Ketone Oxime in Manganese Phosphinate and Phosphonate Chemistry

Cited by 17 publications

References 77 publications

Selective Formation, Reactivity, Redox and Magnetic Properties of MnIII and FeIII Dinuclear Complexes with Shortened Salen-Type Schiff Base Ligands

Selective Formation, Reactivity, Redox and Magnetic Properties of MnIII and FeIII Dinuclear Complexes with Shortened Salen-Type Schiff Base Ligands

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Various Silver Phosphinate Inorganic Architectures in Three-Dimensional Frameworks with Argentophilic Interactions

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