A new two-dimensional extended adenine and thiophenecarboxylate mixed-ligand zinc(II) complex: synthesis, structure, thermostability and luminescent properties

Acta Crystallogr C Struct Chem. 2015 Dec 1;71(Pt 12):1069-73. doi: 10.1107/S2053229615021221. Epub 2015 Nov 12.

Abstract

The design and preparation of crystalline polymeric materials has attracted increasing attention due to their diverse applications as functional materials in gas storage, separation, catalysis, sensing and photoluminescence. The judicious selection of organic linkers is critical for varying the coordination behaviour of the metal ions and determining the overall characteristics of the networks. A new adenine-based Zn(II) coordination polymer, [Zn(C6H2O4S)(C5H5N5)]n or [Zn(tdc)(9H-ade)] (H2tdc is thiophene-2,5-dicarboxylic acid and ade is adenine), has been prepared hydrothermally and the crystal structure exhibits in its packing two-dimensional (4,4) grid sheets parallel to the ab plane, featuring two distinct square cavities delimited by the two types of ligands and the Zn(II) ions with the dimensions 6.6 × 6.6 and 10.2 × 10.2 Å (based on the Zn...Zn distance). The title complex shows enhanced photoluminescence at 378 nm compared to the free ligands, suggesting that the coordination of H2tdc or adenine to the metal centre effectively increases the rigidity of the ligands and reduces the energy loss by radiative decay of intraligand excited states.

Keywords: adenine; crystal structure; fluorescence; functional materials; hydrogen bonding; metal–organic frameworks (MOFs); thiophene-2,5-dicarboxylic acid; two-dimensional coordination polymer; zinc(II).