A Novel Two‐dimensional Coordination Polymer based on Rhombic Tetrameric Subunit Zn₄O₄ as Building Block

Abstract

Hydrothermal reaction of olsalazine sodium, phenanthroline and Zn(ClO4)2·6H2O in the presence of water and ethanol affords a two‐dimensional coordination polymer [Zn4(OSA)3(Phen)2(H2O)2]n (1) (OSA = olsalazine) which is characterized by single X‐ray determination, IR and UV spectrum. The local coordination around all zinc ions can be best described as a slightly distorted triangle bipyramid. Complex 1 consists of a tetrameric subunit, which is made up of four Zn atoms bridged by four O atoms. Two types of osalazine ligands can be found in the complex according to their different coordination modes of carboxyl groups. Crystal data for 1: $\rm P{\bar 1}$, a = 10.087(7), b = 12.830(9), c = 14.545(11) Å, α =114.598(10)°, β = 92.552(10)°, γ = 108.515(10)°, V = 1588(2) Å3, Z = 2, R1 = 0.0818, wR2 = 0.1855. In comparison with the free ligand, the UV spectrum of 1 in solution (H2O: EtOH = 1:1) shows a small Einstein shift probably due to the formation of coordination polymer and supramoleculer hydrogen‐bonding interactions.

Tweaking the affinity of aryl‐substituted diazosalicylato‐ and pyridine ligands towards Zn (II) and its neighbors in the periodic system of the elements, Cu (II) and Cd (II), and their antimicrobial activity

“…Replacing the phenyl substituent by para ‐substituted aryl or pyridyl groups allows generating a large number of ligands, H 2 L XASA , which in combination with diverse secondary ligands have been used previously for complexation with Zn (II) ions, e.g., [Zn (HL ASA ) 2 (3,5‐dimethylpyrazole) 2 ], {[Zn(HL PASA ) 2 (H 2 O) 2 ]·2DMF} n , [Zn(HL ASA ) 2 (H 2 O) 2 ]·2(2‐methylquinoline) and [Zn 3 (HL SASA ) 2 (Py) 2 (H 2 O) 8 ] n (HL ASA = 5‐[( E )‐2‐phenyl‐1‐diazenyl]‐2‐hydroxybenzoate, HL PASA = 5‐[( E )‐2‐(4‐pyridyl)‐1‐diazenyl]‐2‐hydroxybenzoate, HL SASA = 5‐[( E )‐2‐(4‐sulfophenyl)‐1‐diazenyl]‐2‐hydroxybenzote). These complexes are mononuclear, but with the twofold functionalized pro‐ligand 5‐[( E )‐2‐(3‐carboxy‐4‐hydroxyphenyl)diazen‐1‐yl]‐2‐hydroxybenzoic acid (H 4 L ABisSA ) oligo‐ and polynuclear clusters are also known, which include [Zn 4 (HL ABisSA ) 3 (1,10‐phenanthroline) 2 (H 2 O) 2 ] n with a rhombic tetrameric Zn 4 O 4 core and [Zn 6 (L ABisSA ) 3 (4,4′‐bipyridine) 3 (H 2 O) 4 ]·4DMF with a Zn 6 ‐aggregate . The 1D coordination polymer [Zn(H 2 L ABisSA )(H 2 O) 4 ] n has a mononuclear ZnO 6 coordination environment .…”