A Redox‐Induced Spin‐State Cascade in a Mixed‐Valent Fe<sub>3</sub>(μ<sub>3</sub>‐O) Triangle

Govor, Evgen V.; Al-Ameed, Karrar; Chakraborty, Indranil; Coste, Carla S.; Govor, Olena; Sanakis, Yiannis; McGrady, John E.; Raptis, Raphael G.

doi:10.1002/anie.201610534

Cited by 10 publications

(10 citation statements)

References 42 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…57 Fe-Mössbauer Mössbauer spectra were collected from powdered samples of 20 and reduced product at 80 K. Representative spectra are shown inFigure 62. Spectrum is similar to other [Fe 3 (μ 3 -O)(4-NO 2 -pz) 6 L 3 ] 2-(L = Cl -, Br -, SCN -, py, 4-Me-py) complexes, characterized by quadrupole doublets [33][34][35]. The spectra for 20 is highly characteristic of high-spin ferric ions, with an isomer shift, δ = 0.45 mms -1 and quadrupole splitting ΔE Q = 1.05 mms -1 .…”

supporting

confidence: 75%

See 1 more Smart Citation

Mapping of the Chromium and Iron Pyrazolate Landscape

Plá¹,

Maria²

View full text Add to dashboard Cite

I dedicate this dissertation to my family. Without their perseverance, understanding, unconditional support, and most of all love, the completion of this work would not have been possible. v ACKNOWLEDGMENTS First, I would like to thank my advisor Professor Raphael G. Raptis. This work would have not been possible without his expertise and vast knowledge. Even with many tall walls on the path, he never gave up on my ability to complete this task. His patience and motivation helped me persevere and strive for the best. I am honored to have such a prominent and professional advisor.

show abstract

supporting

confidence: 75%

“…26,27 Pyrazoles are heterocyclic aromatic rings consisting of three carbon atoms and 32 ; they only differ in their magnetic properties, as a result of structural differences from the bridging ligands. [32][33][34][35] Figure 4. Trinuclear Pd II complexes with μ-pz (left) and μ-O 2 CR (right) ligands.…”

Section: Iron Complexes As Active Site Modelsmentioning

confidence: 99%

Mapping of the Chromium and Iron Pyrazolate Landscape

Plá¹,

Maria²

View full text Add to dashboard Cite

show abstract

“…Single crystals suitable for XRD were obtained by a vapor diffusion of petroleum ether into a concentrated solution of product in toluene at room temperature overnight. 1 C,67.89;H,7.42;N,9.21;Found: C,68.34;H,6.54;N,9.98. Note: These combustion results represent the most consistent data we have obtained.…”

Section: Synthesesmentioning

confidence: 97%

“…While Fe(II) complexes feature prominently in spin-crossover applications, 8 examples where spin-crossover can be triggered by redox events are still uncommon. 9 Single crystals suitable for X-ray diffraction were grown by vapor diffusion of diethylether into concentrated acetonitrile solutions. The SXRD structure obtained from crystals grown in this way shows a pseudo-octahedral geometry, with an acetonitrile adduct in the previously open coordination site trans to the pyrrole N to give the solvento adduct 2-MeCN (Figure 1).…”

mentioning

confidence: 99%

See 1 more Smart Citation

Iron(II) Complexes Featuring a Redox‐Active Dihydrazonopyrrole Ligand

Jesse

Chang

Filatov

et al. 2021

Zeitschrift anorg allge chemie

View full text Add to dashboard Cite

Nature uses control of the secondary coordination sphereto facilitate an astounding variety of transformations.Similarly, synthetic chemists have found metal-ligand cooperativity to be a powerful strategy for designing complexes that can mediate challenging reactivity. In particular, this strategy has been used to facilitate two electron reactions with first row transition metals thatmore typically engage in one electron redox processes. While NNN pincer ligands feature prominently in this area, examples which can potentially engage in both proton and electron transfer are less common. Dihydrazonopyrrole (DHP) ligands have been isolated in a variety of redox and protonation states when complexed to Ni. However, the redox-state of this ligand scaffold is less obvious whencomplexed to metal centers with more accessible redox couples. Here, we synthesize a new series of Fe-DHP complexes in two distinct oxidation states. Detailed characterization supports that the redox chemistryin this set is still primarily ligand based. Finally, thesecomplexes exist as 5-coordinate species with an open coordination site offering the possibility of enhanced reactivity.File list (3) download file view on ChemRxiv Manuscript.pdf (1.66 MiB) download file view on ChemRxiv TOC.tif (647.29 KiB) download file view on ChemRxiv SI.pdf (909.39 KiB)

show abstract

Magnetic Exchange Coupling in Macrocyclic Cobalt (II) Complexes: The Influence of Bridging Ligands and Choice of the Computational Methodologies

Almansori,

AI‐Ameed,

Obies

et al. 2023

ChemistrySelect

View full text Add to dashboard Cite

Exchange‐coupled spin states of cobalt complexes represent the key to understanding the challenging nature of the magnetism of cobalt dimer. In this study, we introduce a comprehensive investigation of the nature of magnetic super‐exchange coupling interactions between two metallic centers in a macro ligand cobalt dimer. More importantly, we provide a detailed comparison between a series of bridging ligands and study their role in the magnetic exchange coupling constant in cobalt dimer with tetraaza macrocycle ligand scaffold. By varying the types of bridging and terminal ligands, we explored the nature of magnetic coupling in 24 species of cobalt dimers, which allowed us to draw a magneto‐structure relationship and monitor the effect of bridging/terminal ligands on the overall magnetism. We employed different density functional theory (DFT) methodologies and complete active space self‐consistent field (CASSCF) in our investigation. The results show that there are comprehensible functional dependencies, and the choice of exchange‐correlation functional is critical for calculating the magnetic properties. Using the experimental values of the exchange coupling, we found that hybrid functionals with 10–20 % Hartree‐Fock exchange integrals give acceptable accuracy. Furthermore, we adjusted the percentage of HF integrals to estimate the optimum value required to be included in the hybrid functionals. Finally, we used CASSCF to gain deeper understanding of the magnetic coupling for the valence magnetic electrons and to achieve the true ground state wavefunction, which is not feasible with conventional DFT calculations. However, the CASSCF calculations poorly underestimate the magnetic coupling, which can be significantly improved by including the dynamic correlations, as implemented in the NEVPT2 methodology.

show abstract

A Redox‐Induced Spin‐State Cascade in a Mixed‐Valent Fe₃(μ₃‐O) Triangle

Cited by 10 publications

References 42 publications

Mapping of the Chromium and Iron Pyrazolate Landscape

Mapping of the Chromium and Iron Pyrazolate Landscape

Iron(II) Complexes Featuring a Redox‐Active Dihydrazonopyrrole Ligand

Magnetic Exchange Coupling in Macrocyclic Cobalt (II) Complexes: The Influence of Bridging Ligands and Choice of the Computational Methodologies

Contact Info

Product

Resources

About

A Redox‐Induced Spin‐State Cascade in a Mixed‐Valent Fe3(μ3‐O) Triangle

Cited by 10 publications

References 42 publications

Mapping of the Chromium and Iron Pyrazolate Landscape

Mapping of the Chromium and Iron Pyrazolate Landscape

Iron(II) Complexes Featuring a Redox‐Active Dihydrazonopyrrole Ligand

Magnetic Exchange Coupling in Macrocyclic Cobalt (II) Complexes: The Influence of Bridging Ligands and Choice of the Computational Methodologies

Contact Info

Product

Resources

About

A Redox‐Induced Spin‐State Cascade in a Mixed‐Valent Fe₃(μ₃‐O) Triangle