EPR and ESE of CuS4 complex in Cu(dmit)2: g-Factor and hyperfine splitting correlation in tetrahedral Cu–sulfur complexes

Hoffmann, S. K.; Goslar, J.; Lijewski, Stefan; Zalewska, Alina

doi:10.1016/j.jmr.2013.08.009

Cited by 33 publications

(33 citation statements)

References 43 publications

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“…27,45,46 Moreover, the α 2 value of 0.5 is within the limits calculated by Hoffmann et al 29 for square-planar copper−sulfur complexes The low α 2 value of 1 red indicates a large delocalization of the unpaired electron density onto the sulfur atoms, as it was suggested for other {CuS 4 } complexes. 27,29,45,46 DFT Calculations. To understand the electronic structure of the synthesized complex 1 red , and support the strong covalency of its Cu−S bonds revealed by the EPR experiments, we have carried out DFT calculations.…”

Section: ■ Introductionsupporting

confidence: 87%

One Electron Reduced Square Planar Bis(benzene-1,2-dithiolato) Copper Dianionic Complex and Redox Switch by O₂/HO^–

et al. 2014

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The complex [Ph4P]2[Cu(bdt)2] (1(red)) was synthesized by the reaction of [Ph4P]2[S2MoS2CuCl] with H2bdt (bdt = benzene-1,2-dithiolate) in basic medium. 1(red) is highly susceptible toward dioxygen, affording the one electron oxidized diamagnetic compound [Ph4P][Cu(bdt)2] (1(ox)). The interconversion between these two oxidation states can be switched by addition of O2 or base (Et4NOH = tetraethylammonium hydroxide), as demonstrated by cyclic voltammetry and UV-visible and EPR spectroscopies. Thiomolybdates, in free or complex forms with copper ions, play an important role in the stability of 1(red) during its synthesis, since in its absence, 1(ox) is isolated. Both 1(red) and 1(ox) were structurally characterized by X-ray crystallography. EPR experiments showed that 1(red) is a Cu(II)-sulfur complex and revealed strong covalency on the copper-sulfur bonds. DFT calculations confirmed the spin density delocalization over the four sulfur atoms (76%) and copper (24%) atom, suggesting that 1(red) has a "thiyl radical character". Time dependent DFT calculations identified such ligand to ligand charge transfer transitions. Accordingly, 1(red) is better described by the two isoelectronic structures [Cu(I)(bdt2, 4S(3-,)*)](2-) ↔ [Cu(II)(bdt2, 4S(4-))](2-). On thermodynamic grounds, oxidation of 1(red) (doublet state) leads to 1(ox) singlet state, [Cu(III)(bdt2, 4S(4-))](1-).

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Section: ■ Introductionsupporting

confidence: 87%

One Electron Reduced Square Planar Bis(benzene-1,2-dithiolato) Copper Dianionic Complex and Redox Switch by O₂/HO^–

et al. 2014

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“…250 K) was not as well fitted. Low g values have been observed in other Cu II compounds involving Cu II -S [30] in addition to Cu II complexes, featuring a similar upward turn in susceptibility measurements below 50 K. [29] The anti-ferromagnetic coupling is similar to that reported by others for the square planar Cu 4 II complex of sulfinylcalix [4] arene. [28] Although both acute and obtuse metal-oxo bond angles occur in the molecule, the Hamiltonian reveals that anti-ferromagnetic exchange is dominant.…”

Section: Resultssupporting

confidence: 83%

Magnetic Studies of Metal Ion Coordination Clusters Encapsulated with Thiacalixarene

et al. 2014

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Three thiacalix[4]arene polynuclear complexes have been prepared by literature methods for detailed magnetic investigation. The [Fe 3 O(L) 2 ] (LH 4 ¼ thiacalix[4]arene) complex is found to exhibit interesting anti-ferromagnetic exchange coupling. Jahn-Teller distortion in [Cu 4 (L) 2 ] complex leads to strong anti-ferromagnetic coupling at low temperatures. The temperature-dependent susceptibility of the [(m-H 2 O)Eu 2 (LH) 2 (DMF) 4 ] complex is well described by a ground state involving the thermal population of the lowest three excited states.

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“…244 The best fitting parameters for a simulation of the observed ESR spectra are comparable or consistent with those of related compounds. 195,197,241,242 The ESR spectra under dark conditions can be interpreted as follows. The signals observed for 13 in the dark originate from the spin delocalized over the [Cu(dmit) 2 ] 2¹ anions.…”

Section: Electrical Resistivity and Magnetic Susceptibilitymentioning

confidence: 99%

Development of a Control Method for Conduction and Magnetism in Molecular Crystals

Naito

2016

Bulletin of the Chemical Society of Japan

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This study concerns development of a non-destructive method to control conduction and magnetism of molecular solids such as single crystals of charge-transfer complexes. The method is named “optical doping”, where appropriate irradiation is utilized under ambient conditions. Owing to this feature, it can be applied to a wide range of substances while measuring the properties during the control. In addition, the method adds unique conduction and magnetic properties to common insulators. Unlike other doping methods, optical doping only affects the properties and/or structures of the irradiated part of a sample while leaving the rest of the sample unchanged. There are two patterns in the optical doping. Irreversible optical doping produces junction-structures on the single molecular crystals, which exhibit characteristic behavior of semiconductor devices such as diodes and varistors. Reversible optical doping produces “giant photoconductors” and “photomagnetic conductors” by realizing unprecedented metallic photoconduction. In the latter case, localized spins are also excited to produce a Kondo system, where carriers and localized spins interact with each other. Not only the control of conduction and magnetism, the optical doping has realized the observation of physical properties in molecular crystals hardly observed under any thermodynamic condition.

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EPR and ESE of CuS4 complex in Cu(dmit)2: g-Factor and hyperfine splitting correlation in tetrahedral Cu–sulfur complexes

Cited by 33 publications

References 43 publications

One Electron Reduced Square Planar Bis(benzene-1,2-dithiolato) Copper Dianionic Complex and Redox Switch by O₂/HO^–

One Electron Reduced Square Planar Bis(benzene-1,2-dithiolato) Copper Dianionic Complex and Redox Switch by O₂/HO^–

Magnetic Studies of Metal Ion Coordination Clusters Encapsulated with Thiacalixarene

Development of a Control Method for Conduction and Magnetism in Molecular Crystals

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EPR and ESE of CuS4 complex in Cu(dmit)2: g-Factor and hyperfine splitting correlation in tetrahedral Cu–sulfur complexes

Cited by 33 publications

References 43 publications

One Electron Reduced Square Planar Bis(benzene-1,2-dithiolato) Copper Dianionic Complex and Redox Switch by O2/HO–

One Electron Reduced Square Planar Bis(benzene-1,2-dithiolato) Copper Dianionic Complex and Redox Switch by O2/HO–

Magnetic Studies of Metal Ion Coordination Clusters Encapsulated with Thiacalixarene

Development of a Control Method for Conduction and Magnetism in Molecular Crystals

Contact Info

Product

Resources

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One Electron Reduced Square Planar Bis(benzene-1,2-dithiolato) Copper Dianionic Complex and Redox Switch by O₂/HO^–

One Electron Reduced Square Planar Bis(benzene-1,2-dithiolato) Copper Dianionic Complex and Redox Switch by O₂/HO^–