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Dysprosium Chlorocyanoanilate-Based 2D-Layered Coordination Polymers
- Source :
- Inorganic Chemistry, Inorganic Chemistry, American Chemical Society, 2019, 58 (20), pp.13988-13998. ⟨10.1021/acs.inorgchem.9b01968⟩
- Publication Year :
- 2019
- Publisher :
- HAL CCSD, 2019.
-
Abstract
- A series of two-dimensional (2D)-layered coordination polymers (CPs) based on the heterosubstituted anilate ligand ClCNAn2- derived from 3-chloro-6-cyano-2,5-dihydroxybenzoquinone and DyIII are reported. By changes in the synthetic methods (layering technique, solvothermal or conventional one-pot reactions) and conditions (solvent, concentration, etc.), different types of 2D extended networks could be prepared and structurally characterized. Compounds 1 and 1', two polymorphs with the formula [Dy2(ClCNAn)3(DMSO)6]n·(H2O)x [x = 7 (1), 0 (1')], were prepared by a conventional one-pot reaction and recrystallized at different concentrations. Compound 2, formulated as [Dy2(ClCNAn)3(DMF)6]n, was prepared by a layering technique, while compound 3, formulated as {(Me2NH2)2[Dy2(ClCNAn)4(H2O)2]·(DMF)2·(H2O)5}n, was obtained by a solvothermal method. Compounds 1 and 2 are neutral 2D CPs of the ClCNAn2- ligand and DyIII ions, while 3 presents 2D anionic layers of [Dy2(ClCNAn)4(H2O)2]2- alternating with cationic layers of Me2NH2+ ions. These compounds show very diverse networks, with compound 1 forming 2D (8,3) and (4,3) topology with eight- and four-membered rings with square cavities, 1' and 2, respectively, a 2D (6,3) topology with six-membered rings (a rectangular cavity for 1' and a regular hexagonal cavity for 2), and 3 a 2D (4,4) topology with distorted square cavities. In this respect, 1 and 1' represent the first examples of polymorphism in the family of anilate-based CPs. Thermal analysis measurements (differential scanning calorimetry and thermogravimetry) show an exothermic polymorphic transformation from the kinetically stable 1' phase to the thermodynamically stable phase 1. The magnetic behavior of 1-3 very likely indicates depopulation of the mJ levels, while the presence of weak antiferromagnetic coupling between the DyIII centers mediated by the anilate bridge cannot be excluded.
- Subjects :
- chemistry.chemical_classification
010405 organic chemistry
Cationic polymerization
chemistry.chemical_element
Polymer
[CHIM.MATE]Chemical Sciences/Material chemistry
010402 general chemistry
01 natural sciences
0104 chemical sciences
Inorganic Chemistry
Solvent
Thermogravimetry
Crystallography
Differential scanning calorimetry
chemistry
Polymorphism (materials science)
Dysprosium
[CHIM]Chemical Sciences
[CHIM.COOR]Chemical Sciences/Coordination chemistry
Physical and Theoretical Chemistry
Thermal analysis
ComputingMilieux_MISCELLANEOUS
Subjects
Details
- Language :
- English
- ISSN :
- 00201669 and 1520510X
- Database :
- OpenAIRE
- Journal :
- Inorganic Chemistry, Inorganic Chemistry, American Chemical Society, 2019, 58 (20), pp.13988-13998. ⟨10.1021/acs.inorgchem.9b01968⟩
- Accession number :
- edsair.doi.dedup.....f061591caff7cc68e74f60f5e1641be3