Magnetic properties of the anion-radical salts [M(bipy)3](TCNQ)4·X, where M = Co, Ni, Zn and X = H2O or (CH3)2CO

Šoltésová, D.; Vasylets, G.; Čižmár, E.; Fedorchenko, A. V.; Стародуб, В. А.; Medviediev, Volodymyr V.; Шишкин, Олег В.; Bukrynov, Oleksandr; Feher, A.

doi:10.1016/j.ica.2017.11.001

Inorganica Chimica Acta

2018

DOI: 10.1016/j.ica.2017.11.001

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Magnetic properties of the anion-radical salts [M(bipy)3](TCNQ)4·X, where M = Co, Ni, Zn and X = H2O or (CH3)2CO

D. Šoltésová

G. Vasylets

E. Čižmár

et al.

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2019

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Cited by 2 publications

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“…6,7 On the other hand, the dihedral angle between two pyridyl groups in the bpy ligand (4.0 ) was smaller than those in other Co II -bpy complexes (av. 8.4 , 6.0 -10.1 ), 6,7 in which bpy ligands had contacts with each other. The elongations of two Ru-N bond lengths in our complex might lead to less contact between the co-ligands.…”

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confidence: 79%

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Crystal Structure of <i>cis</i>-Bis(2,2′-bipyridyl)bis(trifluoromethanesulfonato)cobalt(II)

Toyama

Yamamoto

2019

X-ray Structure Analysis Online

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A cobalt(II) complex with two 2,2′-bipyridine (bpy) and two trifluoromethanesulfonato (OTf-) ligands, cis-[Co II (OTf)2(bpy)2], was prepared, and the crystal structure at 173 K was elucidated by the single-crystal X-ray diffraction method. The complex crystallized in the monoclinic space group C2/c with a = 9.90587(16), b = 14.2978(2), c = 18.6626(3)Å, α = 90, β = 101.6670(17), γ = 90 , Z = 4, V = 2588.61(7)Å 3. The R1 and wR2 values were 0.0397 and 0.1016, respectively, for 2377 reflections.

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confidence: 79%

“…These Ru-N bond lengths, 2.1037(19) and 2.0976(18)Å, were longer than those in [Co II (bpy)3] 2+ (av. 2.087 Å, 2.070(2) -2.109(2)Å), 6 and were significantly longer than those in cis-[Co II (OH2)2(bpy)2] 2+ (av. 2.062 Å, 2.058(2) -2.065(2)Å), 7 suggesting that the bpy ligands in our complex were labile.…”

mentioning

confidence: 90%

Crystal Structure of <i>cis</i>-Bis(2,2′-bipyridyl)bis(trifluoromethanesulfonato)cobalt(II)

Toyama

Yamamoto

2019

X-ray Structure Analysis Online

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Stabilization of Pancake Bonding in (TCNQ)₂^.− Dimers in the Radical‐Anionic Salt (N−CH₃−2‐NH₂−5Cl−Py)(TCNQ)(CH₃CN) Solvate and Antiferromagnetism Induction

et al. 2019

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We report a new antiferromagnetic radical‐anion salt (RAS) formed from 7,7,8,8‐tetracyanquinonedimethane (TCNQ) anion and 2‐amino‐5‐chloro‐pyridine cation with the composition of (N−CH 3 −2‐NH 2 −5Cl−Py)(TCNQ)(CH 3 CN). The crystallographic data indicates the formation of (TCNQ) 2 .− radical‐anion π‐dimers in the synthesized RAS. Unrestricted density functional theory calculations show that the formed π‐dimers characterize with strong π‐stacking “pancake” interactions, resulting in high electronic coupling, enabling efficient charge transfer properties, but π‐dimers cannot be stable in the isolated conditions as a result of strong Coulomb repulsions. In a crystal, where (TCNQ) 2 .− π‐dimers bound in the endless chainlets via supramolecular bonds with (N−CH 3 −2‐NH 2 −5‐Cl−Py) + cations, the repulsion forces are screened, allowing for specific parallel π‐stacking interactions and stable radical‐anion dimers formation. Measurements of magnetic susceptibility and magnetization confirm antiferromagnetic properties of RAS, what is in line with the higher stability of ground singlet state of the radical‐anion pair, calculated by means of the DFT. Therefore, the reported radical‐anion (N−CH 3 −2‐NH 2 −5Cl−Py)(TCNQ)(CH 3 CN) solvate has promising applications in novel magnetics with supramolecular structures.

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Magnetic properties of the anion-radical salts [M(bipy)3](TCNQ)4·X, where M = Co, Ni, Zn and X = H2O or (CH3)2CO

Cited by 2 publications

References 27 publications

Crystal Structure of <i>cis</i>-Bis(2,2′-bipyridyl)bis(trifluoromethanesulfonato)cobalt(II)

Crystal Structure of <i>cis</i>-Bis(2,2′-bipyridyl)bis(trifluoromethanesulfonato)cobalt(II)

Stabilization of Pancake Bonding in (TCNQ)₂^.− Dimers in the Radical‐Anionic Salt (N−CH₃−2‐NH₂−5Cl−Py)(TCNQ)(CH₃CN) Solvate and Antiferromagnetism Induction

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Magnetic properties of the anion-radical salts [M(bipy)3](TCNQ)4·X, where M = Co, Ni, Zn and X = H2O or (CH3)2CO

Cited by 2 publications

References 27 publications

Crystal Structure of <i>cis</i>-Bis(2,2′-bipyridyl)bis(trifluoromethanesulfonato)cobalt(II)

Crystal Structure of <i>cis</i>-Bis(2,2′-bipyridyl)bis(trifluoromethanesulfonato)cobalt(II)

Stabilization of Pancake Bonding in (TCNQ)2.− Dimers in the Radical‐Anionic Salt (N−CH3−2‐NH2−5Cl−Py)(TCNQ)(CH3CN) Solvate and Antiferromagnetism Induction

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Magnetic properties of the anion-radical salts [M(bipy)3](TCNQ)4·X, where M = Co, Ni, Zn and X = H2O or (CH3)2CO

Stabilization of Pancake Bonding in (TCNQ)₂^.− Dimers in the Radical‐Anionic Salt (N−CH₃−2‐NH₂−5Cl−Py)(TCNQ)(CH₃CN) Solvate and Antiferromagnetism Induction