Nitrite Reduction by Trinuclear Copper Pyrazolate Complexes: An Example of a Catalytic, Synthetic Polynuclear NO Releasing System

Shi, Kaixiang; Mathivathanan, Logesh; Boudalis, Athanassios K.; Turek, Philippe; Chakraborty, Indranil; Raptis, Raphael G.

doi:10.1021/acs.inorgchem.9b00748

Cited by 24 publications

(19 citation statements)

References 73 publications

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“…), [43,[83][84][85][86][87] and {Cu 3 (m 3 -OH)(m-pz) 3 X 3Ày L y } À1 + y (L = Hpz, py). [84,86] Interestingly,s imilar reactivity was reproduced with the relatedt riazolato [88][89][90] and tetrazolato [91] ligands.…”

Section: Azolatesmentioning

confidence: 99%

“…[148] These discoveries had aknock-on effect in catalysis, by prompting the development of biomimetic catalysts based on such geometries. [87,149]…”

Section: Spin Triangles Of Biological Originmentioning

confidence: 99%

“…Azolato ligands were found to exhibit an even closer structural role with carboxylates, and copper(II) pyrazolate triangles were reported in the 1980s [81, 82] . Pyrazolates have proved to be very productive in providing access to {Cu 3 ( μ 3 ‐E)(μ‐pz) 3 X 3 } 1−/2− structural types, (E −/2− =O 2− , OH − , OR − ; X − =Cl − , NCS − , PhCO 2 − , NO 2 − ), [43, 83–87] and {Cu 3 (μ 3 ‐OH)(μ‐pz) 3 X 3− y L y } −1+ y (L=Hpz, py) [84, 86] . Interestingly, similar reactivity was reproduced with the related triazolato [88–90] and tetrazolato [91] ligands.…”

Section: Variations On a Themementioning

confidence: 99%

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Half‐Integer Spin Triangles: Old Dogs, New Tricks

Boudalis

2021

Chemistry A European J

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Spin triangles, that is, triangularc omplexes of halfinteger spins,a re the oldest molecular nanomagnets (MNMs). Their magnetic properties have been studied long before molecular magnetism was delineated as ar esearch field. This Review presentst he history of their study,w ith references to the parallel developmento fn ew experimental investigations andn ew theoretical ideas used for their interpretation. It then presents an indicative list of spin-triangle familiest oi llustrate their chemical diversity.F inally,i tm akes reference to recent developments in terms of theoretical ideas and new phenomena, as well as to the relevance of spin triangles to spintronic devices and new physics.

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Section: Azolatesmentioning

confidence: 99%

“…[148] These discoveries had aknock-on effect in catalysis, by prompting the development of biomimetic catalysts based on such geometries. [87,149]…”

Section: Spin Triangles Of Biological Originmentioning

confidence: 99%

Section: Variations On a Themementioning

confidence: 99%

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Half‐Integer Spin Triangles: Old Dogs, New Tricks

Boudalis

2021

Chemistry A European J

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“…The reaction of CuCl 2 •2H 2 O, 4-Ph-pzH, NaOH and PPNCl in 6:9:13:1 ratio and approximately 5 mL of various solvents yielded the trinuclear complex, PPN[Cu 3 (µ 3 -OH)(µ-4-Ph-pz) 3 Cl 3 ] [33]. Compound (1) was prepared from the same reagents employing a 6:6:13:1 reagent ratio in a more dilute reaction mixture ( (1) Complex (1) crystallizes in the triclinic space group P1 with the asymmetric unit containing one complete trinuclear and one-half of the mononuclear complex.…”

Section: Synthesismentioning

confidence: 99%

Supramolecular Assemblies of Trinuclear Copper(II)-Pyrazolato Units: A Structural, Magnetic and EPR Study

et al. 2020

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Two anionic complexes, {[Cu3(µ3-OH)(µ-4-Ph-pz)3Cl3]2[Cu(4-Ph-pzH)4](µ-Cl)2}2− (1) and [Cu3(µ3-OH)(µ-pz)3(µ1,1-N3)2(N3)]− (2), crystallize as one-dimensional polymers, held together by weak Cu-(µ-Cl) and Cu-(µ-N3) interactions, respectively. Variable temperature magnetic susceptibility analyses determined the dominant antiferromagnetic intra-Cu3 exchange parameters in the solid state for both complexes, whereas the weak ferromagnetic inter-Cu3 interactions manifested also in the solid state EPR spectra, are absent in the corresponding frozen solution spectra. DFT calculations were employed to support the results of the magnetic susceptibility analyses.

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“…For example, their molecular and magnetic structures make them ideal models for the trimetallic active sites of various bioinorganic systems like the [3Fe‐3S] centres in ferredoxins, or the active sites of particulate methane monoxygenase (pMMO) . Accordingly, their reactivity has also led to their study as biomimetic catalysts . In an entirely different context, triangular systems have been recently proposed as the basis for spintronic materials characterized by spin‐chiral magnetism and magnetoelectric couplings …”

Section: Introductionmentioning

confidence: 99%

Origin of Ferromagnetism and Magnetic Anisotropy in a Family of Copper(II) Triangles

Rogez

Amor

Robert

et al. 2020

Chemistry A European J

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Previously reported ferromagnetic triangles (NnBu 4) 2 [Cu 3 (m 3-Cl) 2 (m-4-NO 2-pz) 3 Cl 3 ] (1), (PPN) 2 [Cu 3 (m 3-Cl) 2 (mpz) 3 Cl 3 ] (2), (bmim) 2 [Cu 3 (m 3-Cl) 2 (m-pz) 3 Cl 3 ] (3) and newly reported (PPh 4) 2 [Cu 3 (m 3-Cl) 2 (m-4-Ph-pz) 3 Cl 3 ] (4) were studied by magnetic susceptometry, electron paramagnetic resonance (EPR) spectroscopy and ab initio calculations to assess the origins of their ferromagnetism and of the magnetic anisotropy of their ground S = 3/2 state (PPN + = bis(triphenylphosphine)iminium, bmim + = 1-butyl-3-methylbenzimidazolium, pz À = pyrazolate). Ab initio studies revealed the d z 2 character of the magnetic orbitals of the compressed trigonal bipyramidal copper(II) ions. Ferromagnetic interactions were attributed to weak orbital overlap via the pyrazolate bridges. From the wavefunctions expansions, the ratios of the magnetic couplings were determined, which were indeterminate by magnetic susceptometry. Single-crystal EPR studies of 1 were carried out to extend the spin Hamiltonian with terms which induce zero-field splitting (zfs), namely dipolar interactions, anisotropic exchange and Dzyaloshinskii-Moriya interactions (DMI). The data were treated through both a giant-spin model and through a multispin exchangecoupled model. The latter indicated that % 62 % of the zfs is due to anisotropic and % 38 % due to dipolar interactions. The powder EPR data of all complexes were fitted to a simplified form of the multispin model and the anisotropic and dipolar contributions to the ground state zfs were estimated.

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Nitrite Reduction by Trinuclear Copper Pyrazolate Complexes: An Example of a Catalytic, Synthetic Polynuclear NO Releasing System

Cited by 24 publications

References 73 publications

Half‐Integer Spin Triangles: Old Dogs, New Tricks

Half‐Integer Spin Triangles: Old Dogs, New Tricks

Supramolecular Assemblies of Trinuclear Copper(II)-Pyrazolato Units: A Structural, Magnetic and EPR Study

Origin of Ferromagnetism and Magnetic Anisotropy in a Family of Copper(II) Triangles

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