1D Cu(II) coordination polymer derived from 2-(2-(2,4-dioxopentan-3-ylidene)hydrazinyl)benzenesulfonate chelator and pyrazine spacer
Highlights
► 1D CuII coordination polymer derived from arylhydrazone of β-diketone (AHBD). ► Pyrazine played crucial role as spacer to form 1D chain. ► A sulfo-group, at ortho-position of AHBD creates additional coordination possibility.
Introduction
For the past two decades, a variety of coordination polymers have received considerable attention due to their rich topologies and interesting functions [1]. One-dimensional coordination polymers (1D CPs), being the simplest topological type of coordination array, represent a good starting point to model and develop strategies for engineering new polymers with useful magnetic, electrical, mechanical, and optical properties [2]. In many cases it is found that the molecules are assembled in a predetermined fashion and prediction of the connectivity of the metal ions and spacer ligands are considered as unprecedented. This is probably due to the poor understanding of the role played by various experimental conditions employed for the growth of a particular crystal and other subtle forces that prevail in the crystal lattice. A rationalization of the synthetic techniques and introduction of new ligands are among the most important directions for CP design.
Arylhydrazones of β-diketones (AHBD) are promising ligands for CP synthesis due to the comparably easy procedure of preparation from cheap and available starting materials combined with their ability to sequester metal ions. Thus, CuII [3], [4], [5], [6], [7], [8], [9], [10], ZnII [11], [12], [13], [14], NiII [4], [15], NaI [16], KI [9], [15], PbII [11], CdII [12], CoII [17] complexes of AHBD with different nuclearities and topologies have been reported. In many AHBD complexes, metal ions possess one or several labile sites, which can be easily replaced by linking agents. Hence, the introduction of a hetero-proligand with bridging potential (e.g. imidazole, ethylenediamine, etc.) allows constructing metal organic frameworks [3], [6], [10]. The hetero-proligands affect the complexation process and drive the overall geometry via coordination, template condensation, deprotonation, etc. thus regulating the primary structure and supramolecular arrangement.
In this connection, herein we report a development of the mentioned strategy and describe the synthesis and structure of a 1D CuII coordination polymer constructed by using known 2-(2-(2,4-dioxopentan-3-ylidene)hydrazinyl)benzenesulfonic acid (H2L) [6] and pyrazine (pz) ligands.
Section snippets
Materials and instrumentation
All the chemicals were obtained from commercial sources (Aldrich) and used as received. The water used for all preparations and analyses was bidistilled and deionised. Infrared spectra (4000–400 cm−1) were recorded on a BIO-RAD FTS 3000MX instrument in KBr pellets. Carbon, hydrogen, and nitrogen elemental analyses were carried out by the Microanalytical Service of the Technical University of Lisbon. Electrospray mass spectra were run with an ion-trap instrument (Varian 500-MS LC Ion Trap Mass
Synthesis
Earlier it was demonstrated [10] that application of 2-(2-(4,4-dimethyl-2,6-dioxocyclohexylidene)hydrazinyl)benzene-sulfonic acid as a chelator and pz as a potential spacer, upon reaction with Cu(NO3)2·2.5H2O, yields a Cu(II) dinuclear complex bridging with pz (Scheme 1). Further polymerization was probably hampered by the steric hindrance by the dimedone fragment of the ligand. Thereafter, we decided to modify the chelating ligand, in particular by introducing an acyclic β-diketone fragment
Conclusions
In this work we have been successfully used a AHBD chelating ligand H2L bearing an acyclic β-diketone fragment and a sulfo-group in ortho-position of the arylhydrazone part, and a pz spacer to synthesize a new Cu(II) 1D coordination polymer. The bidentate pz spacer links binuclear [Cu2(μ-L)2(H2O)2] units, while extensive hydrogen bonding stabilizes the overall supramolecular 3D assembly. It is shown that structural modification of the AHBD chelator allows diversification of the Cu(II)-AHBD-pz
Acknowledgements
This work has been partially supported by the Foundation for Science and Technology (FCT), Portugal, and its PPCDT (FEDER funded) and “Science 2007” programs. K.T.M. and M.N.K. express gratitude to the FCT for a post-doc fellowship and working contracts.
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