Metal-Organic Frameworks of Cobalt(II) with 4,7-Di(1,2,4-triazol-1-yl)-2,1,3-benzothiadiazole and Aromatic Dicarboxylic Acids: Synthesis, Crystal Structures, and Magnetic Properties

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Abstract

The reactions of cobalt(II) nitrate with 4,7-di(1,2,4-triazol-1-yl)-2,1,3-benzothiadiazole (Tr2btd) and aromatic dicarboxylic acids (terephthalic (H2bdc), 2,6-naphthalenedicarboxylic (2,6-H2Ndc), and 2,5-furandicarboxylic (2,5-H2Fdc) acids) afford metal-organic frameworks [Co(Tr2btd)(bdc)]n (I) and {[Co2(Tr2btd)(Dmf)(2,6-Ndc)2]·Dmf}n (II) with the layered structures and chain metal-organic framework [Co(Tr2btd)2(H2O)(2,5-Fdc)]n (III). Compounds I and III are paramagnetic in a temperature range of 1.77–300 K without exchange interactions between the Co2+ cations, and compound II exhibits the antiferromagnetic interaction between the Co2+ cations in the binuclear building blocks with the exchange interaction constant J ≈ −100 K. Single crystals of the phase of compound IIIa with the identical composition but different structure are found when taking samples for X-ray diffraction (XRD) analysis. The molecular structures of metal-organic frameworks I, II, III, and IIIa are determined by XRD (CIF files CCDC nos. 2343141 (I), 2343297 (II), 2343296 (III), and 2343140 (IIIa)).

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About the authors

D. I. Pavlov

Novosibirsk State University; Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences

Email: potapov@niic.nsc.ru
Russian Federation, Novosibirsk; Novosibirsk

A. N. Lavrov

Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences

Email: potapov@niic.nsc.ru
Russian Federation, Novosibirsk

D. G. Samsonenko

Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences

Email: potapov@niic.nsc.ru
Russian Federation, Novosibirsk

A. S. Potapov

Novosibirsk State University; Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences

Author for correspondence.
Email: potapov@niic.nsc.ru
Russian Federation, Novosibirsk; Novosibirsk

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Supplementary files

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2. Scheme 1.

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3. Fig. 1. Thermogravimetric analysis curves of compounds I-III.

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4. Fig. 2. Calculated (bottom) and experimental (top) powder diffractograms of compounds I (a), II (b) and III (c).

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5. Fig. 3. Crystal structure of compound I: fragment of the coordination polymer layer (a); concatenation of neighboring layers (b); packing of layers with π-π interactions between 2,1,3-benzothiadiazole cycles (c).

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6. Fig. 4. Crystal structure of compound II: bi-nuclear secondary building block (a); fragment of the coordination polymer layer (b); packing of layers with π-π interactions between 2,1,3-benzothiadiazole and naphthalene cycles (c).

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7. Fig. 5. Crystal structure of compounds III and IIIa: independent part of the structure of III (a); chain fragment of coordination polymer III (b); packing of neighboring chains of coordination polymer III (c); chain fragment of coordination polymer IIIa (d).

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8. Fig. 6. Magnetic properties of compound III: temperature dependences of paramagnetic component of magnetic susceptibility χp measured in magnetic fields H = 1, 10 kE (a); temperature dependences of inverse susceptibility 1/χp and effective magnetic moment эфф per one cobalt ion calculated in the approximation of non-interacting ions (θ = 0) (b).

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9. Fig. 7. Magnetic properties of compound I: temperature dependences of the paramagnetic component of magnetic susceptibility χp measured in a magnetic field H = 10 kE and effective magnetic moment eff per one cobalt ion calculated in the approximation of non-interacting ions (θ = 0), open circles show the values of эфф after subtracting the contribution of the FM phase with Curie temperature Tc ~ 50 K (a); field dependences of magnetization M measured at T = 1. 77 K, and the normalized magnetic susceptibility χ corrected for the ferromagnetic contribution (filled circles) (b); the dashed line in figure (b) shows the approximation of the data by the Brillouin function for S = 3/2, g = 2.44; the χ(H)/χ(0) data for compound III (open triangles) are shown for comparison.

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10. Fig. 8. Magnetic properties of compound II: temperature dependences of the paramagnetic component of magnetic susceptibility χp measured during thermocycling in a magnetic field H = 0. 1 kE and during cooling in the field H = 10 kE (a); temperature dependence of the effective magnetic moment эфф per formula unit calculated in the approximation of non-interacting molecules (θ = 0), the dashed line shows the approximation of experimental data by the model of AFM-dimers Co2+-Co2+ (J/kB ≈ -100 K) taking into account the splitting of ion levels in the zero field (D/kB = 55 K) (b).

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