Pentacoordinated cloro-bis-o-iminosemiquinonato Mn  and Fe  complexes

Piskunov, A. V.; Pashanova, Kira I.; Ershova, Irina V.; Bogomyakov, A. S.; Smolyaninov, I. V.; Starikov, А. G.; Кубрин, С. П.; Fukin, Georgy K.

doi:10.1016/j.molstruc.2018.03.091

Cited by 20 publications

(12 citation statements)

References 52 publications

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“…The density functional theory (DFT) calculations were performed using the Gaussian 09 program package with the standard 6‐311++G(d,p) basis set including diffuse and polarization functions at all atoms. As it was shown in the previously published works, depending on the central ion, the type of the magnetic bistability mechanism resulting in switching the magnetic characteristics, and the presence of charge of the complex, the best agreement with the experiment is achieved when using hybrid functionals UB3LYP* or UTPSSh . Due to the electroneutrality of the modeled compounds, all the calculations were performed with the use of modified UB3LYP functional—UB3LYP* .…”

Section: Methodsmentioning

confidence: 89%

Rational Design of Electronically Labile Dinuclear Fe and Co complexes with 1,10‐Phenanthroline‐5,6‐Diimine: A DFT study

2019

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A series of coordination compounds of redox‐active 1,10‐phenanthroline‐5,6‐diimine with CoII bis‐diketonates and FeII dihydrobis(pyrazolyl)borates has been computationally designed by means of density functional theory (DFT UB3LYP*/6‐311++G(d,p)) calculations of their electronic structure, energy characteristics, and magnetic properties. Four types of complexes differing by the nature and position of the terminal metal‐centered fragments have been considered. The performed systematic calculations have revealed the systems capable of undergoing thermally initiated spin‐state switching rearrangements, including those governed by the synchronized mechanisms of spin crossover and valence tautomerism. The predicted magnetic characteristics allow one to consider the dinuclear cobalt complexes and heterometallic Co/Fe compounds with 1,10‐phenanthroline‐5,6‐diimine as building blocks for molecular and quantum electronics devices. © 2019 Wiley Periodicals, Inc.

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Section: Methodsmentioning

confidence: 89%

Rational Design of Electronically Labile Dinuclear Fe and Co complexes with 1,10‐Phenanthroline‐5,6‐Diimine: A DFT study

2019

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“…Complex of iron(III) ( Me imSQ) 2 FeBr based on 4,6-di-tert-butyl-N-(2,6-dimethyl-phenyl)-o-aminophenol has been prepared as described previously. [20,44] Figure 1a shows the schematic structure of the complex.…”

Section: Resultsmentioning

confidence: 99%

“…For example, hexacoordinated tris‐o‐iminosemiquinonates (imSQ) 3 Fe, [21] (where imSQ=radical‐anionic o‐iminosemiquinone) undergoes a spin‐crossover between S Fe =5/2→1/2. In contrast SCO transition between high‐spin HS (S Fe =5/2) and intermediate‐spin IS (S Fe =3/2) is observed for ferric pentacordinated (imSQ) 2 FeHal [19,20] (Hal=halogen atom). In both cases spin‐transitions are complicated with strong intramolecular magnetic interactions, which results in changes of the ground states of molecules [43] …”

Section: Introductionmentioning

confidence: 94%

“…[16,17] Moreover, o-benzoquinone and o-iminobenzoquinone complexes were found to demonstrate a spin-crossover effect [18][19][20][21][22][23] and different types of inter-or intramolecular magnetic exchange interactions. [18][19][20][21]24,25] The application of radical-ionic ligands as spin labels in metal complexes allows one to examine their composition, structure and dynamic processes by means of electron paramagnetic resonance spectroscopy. [26][27][28] On the other hand, redox ligands can be used as reservoirs of electrons for bond-making and bond-breaking reactions.…”

Section: Introductionmentioning

confidence: 98%

“…Detailed investigation of magnetic properties, electrochemical and spectroscopic features allowed ones to discover such unique phenomena as redox‐isomerism (or valence‐tautomerism), [3,8–15] photo and termomechanical effects [16,17] . Moreover, o‐benzoquinone and o‐iminobenzoquinone complexes were found to demonstrate a spin‐crossover effect [18–23] and different types of inter‐ or intramolecular magnetic exchange interactions [18–21,24,25] . The application of radical‐ionic ligands as spin labels in metal complexes allows one to examine their composition, structure and dynamic processes by means of electron paramagnetic resonance spectroscopy [26–28] …”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Structural Changes in Five‐Coordinate Bromido‐bis(o‐iminobenzo‐semiquinonato)iron(III) Complex: Spin‐Crossover or Ligand‐Metal Antiferromagnetic Interactions?

et al. 2021

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Spin-crossover metal complexes represent important building blocks for a future generation of electronic and optical devices. Pentacoordinated o-iminosemiquinonate iron(III) complexes are able to demonstrate spin transitions between high spin (HS) and intermediate spin (IS) states under the influence of temperature or irradiation. Studied (Me imSQ) 2 FeBr sample showed a broad magnetic transition in the temperature region from 30 K to 300 K. Remarkably that observed behavior of magnetization can be interpreted with two controversial models. In the first model, the values of the effective magnetic moment at low temperature and high temperature can be assigned to the IS and HS magnetic moment of ferric ion coupled antiferromagnetically to radical anion ligands. In the second model, the metal spin on metal center remains IS in the whole temperature interval, while the mutual orientation of three magnetic moments in the molecule undergo changes due to exchange interactions. In this work we apply density functional theory and X-ray absorption spectroscopy to unravel the origin of magnetic properties of the complex. Temperature-induced changes of interatomic distances in the first coordination sphere support the second model. Such comprehensive analysis of the magnetic properties makes it possible to shed light on the nature of spin transitions in complexes of transition metals with open-shell ligands, which are often complicated by strong exchange interactions.

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Spin‐State‐Switching Rearrangements of Bis(dioxolene)‐Bridged CrCo Complexes: A DFT Study

et al. 2021

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Density functional theory calculations (UTPSSh/6-311 + + G-(d,p)) of electronic structure, energy characteristics and magnetic properties of a series of heterometallic CrCo complexes comprising redox-active bis(dioxolene) bridging ligands (3,3,3',3'-tetramethyl-5,6,5',6'-tetrahydroxy-1,1'-spiro-bis(indan) and 2,3,6,7-tetrahydroxy-9,10-dimethyl-9,10-dihydro-9,10-ethanoanthracene) and ancillary tetradentate nitrogen-containing bases (tris(2-pyridylmethyl)amine and N,N'-dialkyl-2,11-diaza [3.3]-(2,6)pyridinophane derivatives) were performed. The compounds prone to manifest spin-state switching rearrangements involving cobalt centre have been revealed. Analysis of the results obtained and their comparison with those found previously open wide prospects for the purposeful search for a broad variety of new magnetically bistable heterometallic dinuclear paramagnetic species with a prospect of useful application in the design of smart dynamic materials.

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Pentacoordinated cloro-bis-o-iminosemiquinonato Mn and Fe complexes

Cited by 20 publications

References 52 publications

Rational Design of Electronically Labile Dinuclear Fe and Co complexes with 1,10‐Phenanthroline‐5,6‐Diimine: A DFT study

Rational Design of Electronically Labile Dinuclear Fe and Co complexes with 1,10‐Phenanthroline‐5,6‐Diimine: A DFT study

Structural Changes in Five‐Coordinate Bromido‐bis(o‐iminobenzo‐semiquinonato)iron(III) Complex: Spin‐Crossover or Ligand‐Metal Antiferromagnetic Interactions?

Spin‐State‐Switching Rearrangements of Bis(dioxolene)‐Bridged CrCo Complexes: A DFT Study

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