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CrIII–CrIII interactions in two alkoxo-bridged heterometallic Zn2Cr2 complexes self-assembled from zinc oxide, Reinecke's salt and diethanolamine.

Autorzy

V. V. Semenaka

Oksana V. Nesterova

Vladimir N. Kokozay

Viktoriya V. Dyakonenko

R. I. Zubatyuk

Oleg V. Shishkin

Roman Boča

Julia Jezierska

Andrew Ozarowski

Rok wydania

2010

Czasopismo

Inorganic Chemistry

Numer woluminu

49

Strony

5460-5471

DOI

10.1021/ic1000123

Kolekcja

Naukowa

Język

Angielski

Typ publikacji

Artykuł

Streszczenie

Two new tetranuclear complexes, [Zn2Cr2(NCS)4(Dea)2(HDea)2]·4DMSO (1; DMSO = dimethyl sulfoxide) and [Zn2Cr2(NCS)4(Dea)2(HDea)2]·2CH3CN (2), were prepared from zinc oxide, Reinecke’s salt, NH4[Cr(NCS)4(NH3)2]·H2O, ammonium thiocyanate, and a nonaqueous solution of diethanolamine (H2Dea) in a reaction carried out under open air. Both compounds have similar centrosymmetric crystal structures based on a tetranuclear {Zn2Cr2(μ3-O)2(μ-O)4} core. Variable-temperature magnetic susceptibility measurements of 1 and 2 show weak antiferromagnetic coupling between chromium centers. The magnetic data and high-field, high-frequency electron paramagnetic resonance spectra were analyzed in terms of the spin Hamiltonianwith J = 13.7 cm−1, j = 1.1 cm−1, DCr = 0.3864 cm−1, ECr = −0.1104 cm−1, D12 = −0.1873 cm−1, and E12 = −0.0155 cm−1 for 1 and J = 9.4 cm−1, j = 0.8 cm−1, DCr = 0.3564 cm−1, ECr = −0.0647 cm−1, D12 = −0.1850 cm−1, and E12 = −0.0112 cm−1 for 2. Density functional theory (DFT) calculations were employed to calculate the zero-field splitting on Cr3+ ions. Calculations of the exchange integrals J were attempted by using the “broken-symmetry” DFT method.

Adres publiczny

https://doi.org/10.1021/ic1000123

Strona internetowa wydawcy

https://www.acs.org/content/acs/en.html

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