期刊
INORGANIC CHEMISTRY
卷 61, 期 30, 页码 11651-11666出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.2c01241
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Three copper(II)/mesoxalate-based MOFs were synthesized with different arrangements of cations, which have a significant impact on the proton conduction of the materials. These compounds also exhibit antiferromagnetic coupling.
Three copper(II)/mesoxalate-based MOFs with formulas (H3O)[Cu-9(Hmesox)(6)(H2O)(6)Cl]center dot 8H(2)O (1), (NH2Me2)(0.4)(H3O)(0.6)[Cu-9(Hmesox)(6)(H2O)(6)Cl]center dot 8H(2)O (2), and (enH(2))(0.25)(enH)(1.5)[Cu-6(Hmesox)(3)(mesox)(H2O)(6)Cl-0.5]Cl-0.5 center dot 5.25H(2)O (3) were synthesized (H(4)mesox = mesoxalic acid = 2,2-dihydroxypropanedioic acid, en = ethylenediamine). Essentially, all of the compounds display the same anionic network with a different arrangement of the cations, which have a remarkable effect on the proton conduction of the materials, ranging from 1.16 x 10(-4) S cm(-1) for 1 to 1.87 x 10(-3) S cm(-1) for 3 (at 80 degrees C and 95% RH). These compounds also display antiferromagnetic coupling among the copper(II) ions through both the carboxylate and alkoxido bridges. The values of the principal magnetic coupling constants were calculated by density functional theory (DFT), leading to congruent values that confirm the predominant antiferromagnetic nature of the interactions.
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