Self-assembled 3D heterometallic Zn(II)/K(I) metal–organic framework with the fluorite topology
Graphical abstract
Self-assembly generation and structural features of a novel heterometallic Zn(II)/K(I) metal–organic framework have been investigated.
Introduction
Despite a very intense research in recent years on homometallic coordination polymers (CPs) or metal–organic frameworks (MOFs), the synthesis and characterization of heterometallic CPs or MOFs has been explored to a lesser extent. However, such coordination compounds attracted a considerable attention in the areas of crystal growth and design, inorganic and material chemistry, what is primarily governed by structural diversity and potential applications of such materials in view of possible synergic effects of different metal atoms [1], [2], [3], [4], [5], [6], [7], [8], [9], [10].
In particular, heterometallic coordination polymers and metal–organic frameworks based on Zn2+ and alkali metal ions (e.g., Na+, K+) represent an interesting class of compounds in view of biological and/or physiological importance of these metals, as well as notable applications of such compounds in supramolecular chemistry and biomimetic catalysis [11], [12], [13], [14]. Considering these points and following our interest in exploring various ditopic thiocarbazone building blocks in crystal engineering of CPs or MOFs, we have selected in the current work bis(pyridine-2-aldehyde) thiocarbazone (H2L) as a still poorly explored organic building block. Then, a series of reactions between zinc(II) acetate, H2L, and KSCN in methanol has been attempted using a branched tube synthetic method. One of the attempts has been successful and resulted in the self-assembly formation of a novel heterometallic Zn(II)/K(I) metal–organic framework [Zn2(L)K2(µ2-H2O)2(µ2-SCN)4]n (1). Hence, in the present study we describe the preparation, characterization, structural and topological features, and as Hirshfeld surface analysis of compound 1. This compound is the first example of heterometallic Zn(II)/K(I) metal–organic framework derived from bis(pyridine-2-aldehyde) thiocarbazone block (Scheme 1).
Section snippets
Materials and methods
Bis(pyridine-2-aldehyde) thiocarbazone (H2L) was prepared according to the published method [15]. Other reagents and solvents employed were commercially available and used as received. Elemental analysis was performed on a Heraeus CHN-S-Rapid analyzer. IR spectrum was recorded with a Bruker Tensor27 FT-IR spectrometer in the range of 4000–400 cm−1 using crystalline samples on a KBr pellets.
Synthesis and analytical data for[Zn2(L)K2(µ2-H2O)2(µ2-SCN)4]n (1)
Bis(pyridine-2-aldehyde) thiocarbazone (H2L) (0.308 g, 1.08 mmol), Zn(OAc)2·2H2O (0.0576 g, 2.16 mmol) and
Synthesis
In the course of this work, we have attempted a number of reactions by treating bis(pyridine-2-aldehyde) thiocarbazone (H2L) with Zn(OAc)2·2H2O and KSCN in methanol medium. The obtained polycrystalline solids were not soluble in most of the common solvents and we failed to crystallize the materials as single crystals. Thus, a possible solution to overcome our inability to grow single-crystals consisted of using an unusual glassware (apparatus) and reaction/crystallization method that was
Conclusions
This study has shown that our recently developed branched tube method for the synthesis and crystallization of insoluble coordination compounds can be successfully applied for the self-assembly generation of a novel heterometallic zinc(II)/potassium(I) metal–organic framework [Zn2(L)K2(µ2-H2O)2(µ2-SCN)4]n (1). This product was obtained using a still poorly explored ditopic thiocarbazone (H2L) as a principal building block and potassium thiocyanate as ligand and metal source. Structural and
Acknowledgements
We are grateful to the University of Mohaghegh Ardabili and University of Maragheh Research Council for the generous financial support of this research. AMK acknowledges the FCT, Portugal (UID/QUI/00100/2013).
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