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Crystals 2018, 8(1), 7; https://doi.org/10.3390/cryst8010007

Synthesis and Luminescence Properties of New Metal-Organic Frameworks Based on Zinc(II) Ions and 2,5-Thiophendicarboxylate Ligands

1
Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, 3 Lavrentieva Ave., 630090 Novosibirsk, Russia
2
Department of Natural Sciences, Novosibirsk State University, 2 Pirogova Str., 630090 Novosibirsk, Russia
*
Author to whom correspondence should be addressed.
Received: 29 November 2017 / Revised: 21 December 2017 / Accepted: 22 December 2017 / Published: 24 December 2017
(This article belongs to the Special Issue Crystal Structure Analysis of Supramolecular and Porous Solids)
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Abstract

Six new metal-organic frameworks based on 2,5-thiophendicarboxylate (tdc2–) and zinc(II) ions were prepared in different reaction conditions, and their crystal structures were determined by XRD analysis. The compound [Zn(tdc)(dabco)(H2O)]∙DMF (1) is based on mononuclear Zn(II) ions connected by tdc2– and dabco linkers into square-grid layered nets. The compound [Zn3(tdc)3(dabco)2] (2) is a rare example of monocoordinated dabco ligands in the metal-organic framework chemistry. Its crystal structure contains trinuclear linear carboxylate building units, connected into a distorted primitive cubic net. Similar trinuclear units were also found in [Zn5(tdc)4(Htdc)2(dabco)2]∙4DMF∙14H2O (3), although as a part of more complicated pentanuclear motives. The compound [Na2Zn(tdc)2(DMF)2] (4), quantitatively isolated by the addition of NaOH to the mixture of Zn(NO3)2 and H2tdc, is based on 1D chain motives, interconnected by tdc2– linkers into a three-dimensional framework. The compounds [Zn3(tdc)3(DMF)2]∙0.8DMF∙1.1H2O (5) and [Zn3(tdc)3(DMF)3]∙0.8DMF∙1.3H2O (6) were prepared in very similar reaction conditions, but with different times of heating, indirectly indicating higher thermodynamic stability of the three-dimensional metal-organic framework 6, compared to the two-dimensional metal-organic framework 5. The crystal structures of both 5 and 6 are based on the same trinuclear linear units as in 2. Luminescence properties of the compounds 46 were studied and compared with those for Na2tdc salt. In particular, the luminescence spectra of 4 practically coincide with those for the reference Na2tdc, while 5 and 6 exhibit coherent shifts of peaks to higher energies. Such hypsochromic shifts are likely associated with a different effective charge on the tdc2– anions in Na2tdc and sodium-containing 4, compared to zinc-based 5 and 6. View Full-Text
Keywords: metal-organic frameworks; zinc(II) complexes; 2,5-thiophendicarboxylic acid; X-ray diffraction analysis; luminescence metal-organic frameworks; zinc(II) complexes; 2,5-thiophendicarboxylic acid; X-ray diffraction analysis; luminescence
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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Lysova, A.; Samsonenko, D.; Dybtsev, D.; Fedin, V. Synthesis and Luminescence Properties of New Metal-Organic Frameworks Based on Zinc(II) Ions and 2,5-Thiophendicarboxylate Ligands. Crystals 2018, 8, 7.

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