CRYSTAL STRUCTURE OF METAL-ORGANIC FRAMEWORKS BASED ON TERBIUM AND 1,4-NAPHTHALENEDICARBOXYLIC ACID
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CRYSTAL STRUCTURE OF METAL-ORGANIC FRAMEWORKS BASED ON TERBIUM AND 1,4-NAPHTHALENEDICARBOXYLIC ACID M. O. Barsukova,1,2 D. G. Samsonenko,1,2 and V. P. Fedin 1,2*
The interaction of terbium nitrate pentahydrate and 1,4-naphthalenedicarboxylic acid (H2ndc) in a solvent mixture under solvothermal conditions yields two new metal-organic frameworks: ((CH3)2NH2)2[Tb3(H2O)(HCOO)(ndc)5]·3DMF (1) and [Tb4(DMF)(NMP)6(ndc)6] (2) (ndc2– is 1,4naphthalenedicarboxylate, DMF is N,N-dimethylformamide, NMP is N-methyl-2-pyrrolidone). The crystal structures of compounds 1 and 2 are established by the single crystal X-ray diffraction analysis. Compound 1 is a negatively charged 3D framework in which dimethyl ammonium cations act as counterions. The remaining volume available for solvent molecules is filled with DMF. Compound 2 has a dense layered structure. The luminescence spectrum contains one emission band corresponding to π*– π transitions in the ligand. DOI: 10.1134/S0022476620070112 Keywords: terbium, 1,4-naphthalenedicarboxylic acid, metal-organic frameworks, X-ray diffraction analysis.
INTRODUCTION Metal-organic frameworks (MOFs) represent one-, two-, or three-dimensional polymeric regular structures in which inorganic cores consisting of metal cations or clusters are bound by polytopic organic linkers. Possible applications of these compounds involve sorption and separation of molecules [1-3], catalysis [4-6], luminescence [7, 8], and many others. MOFs based on rigid Lewis acids such as lanthanide cations (Sc(III), Y(III), In(III), Ga(III), Al(III)) are of special interest because the materials based on them often have higher hydrolytic and thermal stabilities [9, 10]. Lanthanide-based MOFs not only demonstrate ample opportunities for the structural design and functionalization but also have unique luminescent properties: large Stokes shifts, narrow emission bands, wide color range, and long lifetimes, especially for Tb(III) and Eu(III) [11, 12]. Lanthanide-based MOFs have recently attracted more and more attention as fluorescent sensors to detect cations, anions, and small molecules. This occurs owing to their unique luminescent characteristics as well as high chemical and thermal stabilities [13]. In this work, we describe the synthesis of two new MOFs based on terbium(III) cations and 1,4naphthalenedicarboxylic acid (H2ndc): ((CH3)2NH2)2[Tb3(H2O)(HCOO)(ndc)5]⋅3DMF (1) and [Tb4(DMF)(NMP)6(ndc)6] (2).
1
Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia; *[email protected]. 2Novosibirsk State University, Novosibirsk, Russia. Original article submitted January 16, 2020; revised January 29, 2020; accepted January 30, 2020. 1090
0022-4766/20/6107-1090 © 2020 by Pleiades Publishing, Ltd.
Crystal structures of the synthesized compounds were determined by the single crystal X-ray diffraction analysis. For compound 2 the composition was confirmed by elemental and thermogravimetric (TG) analyses and IR spectroscopy. The luminescent properties of compound 2 were invest
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