Transition Metal Coordination Polymers with Trans-1,4-Cyclohexanedicarboxylate: Acidity-Controlled Synthesis, Structures and Properties

Demakov, Pavel A.; Bogomyakov, A. S.; Urlukov, Artem S.; Andreeva, A. Yu.; Samsonenko, Denis G.; Dybtsev, Danil N.; Fedin, Vladimir P.

doi:10.3390/ma13020486

Cited by 10 publications

(5 citation statements)

References 49 publications

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“…Indeed, the effective magnetic moment µeff formally calculated for 1 gradually decreases from µeff = 4.78 µB at T = 300 K down to µeff = 3.81 µB at T = 1.77 K (Figure 5a). The high-temperature µeff = 4.78 µB agrees well with the values commonly observed for octahedrally coordinated Co 2+ ions with a high-spin configuration (S = 3/2) and a considerable contribution of orbital moments [84]. The strong decrease in the effective magnetic moment obseved on cooling originates predominantly from the zero-field-splitting (ZFS) of Co 2+ ion levels [85].…”

Section: Magnetization Measurementssupporting

confidence: 85%

Flexible Co(II)-and Ni(II)-Based Cationic 2D Metal–Organic Frameworks Based on a Charge-Neutral (O,O)-Donor Bridge

et al. 2023

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Two new metal–organic frameworks based on highly flexible 1,4-diazabicyclo[2.2.2]octane N,N′-dioxide (odabco) ligands were successfully synthesized and characterized. Their crystallographic formulae are [M(DMF)2(odabco)2](ClO4)2·dioxane, where M2+ = Co2+ (1) and Ni2+ (2), and DMF is N,N-dimethylformamide. The title compounds possess cationic 2D coordination networks filled with perchlorate anions and dioxane solvent molecules in the interlayer space, with 20% solvent accessible volume. Carbon dioxide adsorption measurements for desolvated samples 1a and 2a gave 511 m2/g and 377 m2/g specific surface areas, respectively, revealing the first example of gas adsorption properties in the structure based on a flexible odabco bridge, despite the presence of large counteranions within the positively charged network. Magnetization measurements for 1, 1a, 2 and 2a reveal their paramagnetic nature to be in a reasonable agreement with crystal structures, and almost no solvent dependence of the magnetization characteristics. A decrease in the effective magnetic moment observed at low temperatures is attributed mostly to zero-field level-splitting in the octahedral Ni2+ and Co2+ ions.

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Section: Magnetization Measurementssupporting

confidence: 85%

Flexible Co(II)-and Ni(II)-Based Cationic 2D Metal–Organic Frameworks Based on a Charge-Neutral (O,O)-Donor Bridge

et al. 2023

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“…The final weight residue after the second stage is 22% and corresponds well to Cu2O as the final product for the decomposition of I (22.4% theoretical weight) in an inert atmosphere. Such a stepwise shape of the TGA curve is similar to the examples within the literature for other "acidic" trans-1,4-cyclohexanedicarboxylates, such as non-isostructural [Mn2(Hchdc)2(chdc)]n [38].…”

Section: Phase Purity and Characterizationsupporting

confidence: 82%

Synthesis, Structure and Magnetic Properties of Low-Dimensional Copper(II) trans-1,4-cyclohexanedicarboxylate

Demakov,

Ovchinnikova,

Dorovatovskii

et al. 2024

Crystals

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A reaction between copper(II) nitrate and trans-1,4-cyclohexanedicarboxylic acid (H2chdc) carried out under hydrothermal conditions led to a new metal-organic coordination polymer [Cu2(Hchdc)2(chdc)]n. According to single-crystal XRD data, the compound is based on bi-nuclear paddlewheel-type carboxylate blocks that are joined with polymeric chains due to the (μ3-κ1:κ2) coordination of carboxylate groups. The chains are interconnected by chdc2− bridging ligands into layers containing free COOH groups of terminal Hchdc−. The neighboring layers adopt a RCOOH···OOCR hydrogen bond-assisted arrangement into a dense-packed structure. Magnetization measurements showed the presence of a strong antiferromagnetic exchange interaction (J/kB = −495 K) inside the bi-nuclear blocks. At the same time, no significant interaction was found between the {-Cu2(OOCR)4-} units in spite of their polymeric in-chain packing. Patterns of magnetic behavior of [Cu2(Hchdc)2(chdc)]n were thoroughly analyzed and explained from a structural point of view.

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“…As an important branch in the field of supramolecular chemistry and crystal engineering, the design and assembly of metal-organic coordination frameworks (MOFs) or coordination polymers (CPs) have stimulated the interest of chemists over the past few decades [1][2][3][4][5][6][7], not only due to their intriguing network topologies, but also the possible application. Lanthanide coordination polymers (CPs) have been studied due to their applicability in gas storage, catalysis, and luminescence [8][9][10][11][12][13][14][15]. To date, most of the organic ligands used in MOFs chemistry are limited to a rigid aromatic carboxylate containing ligand [16][17][18], whereas the role of a flexible carboxylate ligand is somewhat ignored.…”

Section: Introductionmentioning

confidence: 99%

New Coordination Polymers of Selected Lanthanides with 1,2-Phenylenediacetate Linker: Structures, Thermal and Luminescence Properties

et al. 2021

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Solvothermal reactions of lanthanide (III) salts with 1,2-phenylenediacetic acid in N,N′-dimethylformamide (DMF) solvent lead to the formation of the metal complexes of the general formula Ln2(1,2-pda)3(DMF)2, where Ln(III) = Pr(1), Sm(2), Eu(3), Tb(4), Dy(5), and Er(6), 1,2-pda = [C6H4(CH2COO)2]2−. The compounds were characterized by elemental analysis, powder and single-crystal X-ray diffraction methods, thermal analysis methods (TG-DSC and TG-FTIR), infrared and luminescence spectroscopy. They exhibit structural similarity in the two groups (Pr, Sm, and Eu; Tb, Dy, and Er), which was reflected in their thermal behaviours and spectroscopic properties. Single-crystal X-ray diffraction studies reveal that Sm(2) and Eu(3) complexes form 2D coordination polymers with four crystallographically independent metal centers. Every second lanthanide ion is additionally coordinated by two DMF molecules. The 1,2-phenylenediacetate linker shows different denticity being: penta- and hexadentate while carboxylate groups exhibit bidentate-bridging, bidentate-chelating, and three-dentate bridging-chelating modes. The infrared spectra reflect divergence between these two groups of complexes. The complexes of lighter lanthanides contain in the structure coordinated DMF molecules, while in the structures of heavier complexes, DMF molecules appear in the inner and outer coordination sphere. Both carboxylate groups are deprotonated and engaged in the coordination of metal centers but in different ways in such groups of complexes. In the groups, the thermal decomposition of the isostructural complexes occurs similarly. Pyrolysis of complexes takes place with the formation of such gaseous products as DMF, carbon oxides, ortho-xylene, ethers, water, carboxylic acids, and esters. The complexes of Eu and Tb exhibit characteristic luminescence in the VIS region, while the erbium complex emits NIR wavelength.

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Transition Metal Coordination Polymers with Trans-1,4-Cyclohexanedicarboxylate: Acidity-Controlled Synthesis, Structures and Properties

Cited by 10 publications

References 49 publications

Flexible Co(II)-and Ni(II)-Based Cationic 2D Metal–Organic Frameworks Based on a Charge-Neutral (O,O)-Donor Bridge

Flexible Co(II)-and Ni(II)-Based Cationic 2D Metal–Organic Frameworks Based on a Charge-Neutral (O,O)-Donor Bridge

Synthesis, Structure and Magnetic Properties of Low-Dimensional Copper(II) trans-1,4-cyclohexanedicarboxylate

New Coordination Polymers of Selected Lanthanides with 1,2-Phenylenediacetate Linker: Structures, Thermal and Luminescence Properties

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