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Pillaring of $CdCl_2$-Like Layers in Lanthanide Metal-Organic Frameworks:Synthesis, Structure, and Photophysical Properties

Mahata, Partha and Ramya, KV and Natarajan, Srinivasan (2008) Pillaring of $CdCl_2$-Like Layers in Lanthanide Metal-Organic Frameworks:Synthesis, Structure, and Photophysical Properties. In: Chemistry- A European Journal, 14 (19). pp. 5839-5850.

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A hydrothermal reaction of lanthanide salts, pyridine-2,3-dicarboxylic acid, benzene-1,4-dicarboxylic acid, and water gave rise to a new series of three-dimensional mixed carboxylates (homocyclic and heterocyclic) of lanthanides with the general formula $[M_{2^-}(H_2O_4)][\{C_5H_3N(COO)_2\}_2\{C_6H_4-(COO)_2\}]$, M=La (I), Pr (II), and Nd (III).T he structure consists of M2O14N2 dimeric units connected by pyridine-2,3-dicarboxylate moieties to form twodimensional layers that are pillared by terephthalate units.The structures also possess two coordinated water molecules, which are arranged to form one dimensional helical chains and can be reversibly adsorbed.T he connectivity within the layers closely resembles that of the $CdCl_2$ layered structure with $3^6$ topology.To the best of our knowledge,this is the first observation of $CdCl_2$ topology in lanthanide metal–organic framework compounds.Partial substitution of $La^{3+}$ in I by $Eu^{3+}$ and $Tb^{3+}$ (2 and 4%) gives rise to characteristic red/pink or green emission, which suggests a ligand-sensitized metal-centered emission.T he Nd compound III shows interesting UV and blue emission through an up-conversion process.

Item Type: Journal Article
Publication: Chemistry- A European Journal
Publisher: John Wiley and Sons
Additional Information: Copyright of this article belongs to John Wiley and Sons.
Keywords: carboxylate ligands;hydrothermal;synthesis;lanthanides;luminescence;metal–organic frameworks.
Department/Centre: Division of Chemical Sciences > Solid State & Structural Chemistry Unit
Date Deposited: 07 Aug 2008
Last Modified: 19 Sep 2010 04:48
URI: http://eprints.iisc.ac.in/id/eprint/15479

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