Journal
INORGANIC CHEMISTRY
Volume 48, Issue 11, Pages 4942-4951Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ic9003356
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Funding
- Department of Science and Technology, Government of India
- Council of Scientific and Industrial Research, Government of India
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A new two-dimensional 3d-4f mixed-metal mixed dicarboxylate (homocyclic and heterocyclic) of the formula [Gd-2(H2O)(2)Ni(H2O)(2)(1,2-bdc)(2)(2,5-pydc)(2)]center dot 8H(2)O (1;1,2-H(2)bdc = 1,2-benzenedicarboxylic acid and 2,5-H(2)pydc = 2,5-pyridinedicarboxylic acid) has been prepared by employing the hydrothermal method. The structure has infinite one-dimensional -Gd-O-Gd- chains formed by the edge-shared GdO9 polyhedral units, resulting exclusively from the connectivity between the Gd3+ ions and the 1,2-bdc units. The chains are connected by the [Ni(H2O)(2)(2,5-pydc)(2)](2-) metalloligand, forming the two-dimensional layer arrangements. The stacking of the layers creates hydrophilic and hydrophobic spaces in the interlamellar region. A one-dimensional water ladder structure, formed by the extraframework water molecules, occupies the hydrophilic region while the benzene ring of 1,2-bdc occupies the hydrophobic region. To the best of our knowledge, the present compound represents the first example of a 3d-4f mixed-metal carboxylate in which two different aromatic dicarboxylate anions act as the linkers. The stabilization energies of the water clusters have been evaluated using density functional theory calculations. The water molecules in 1 are fully reversible accompanied by a change in color (greenish blue to brown) and coordination around Ni2+ ions (octahedral to distorted tetrahedral).
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