Rational Design of Metal‐Organic Frameworks Based on 5‐(4‐Pyridyl)tetrazolate: From 2D Grids to 3D Porous Networks

Abstract

Abstract The hydrothermal reactions of Zn(ClO 4 ) 2 ·6H 2 O/Cu(NO 3 ) 2 ·6H 2 O with 5‐(4‐pyridyl)tetrazole in an ethanol/water or ethanol/water/pyridine medium yield one 2D and one 3D metal‐organic coordination framework [Zn 2 (OH)(4‐ptz) 3 ] ( 1 ) and [Cu(4‐ptz)·0.5(py)] ( 3 ) [4‐ptz = 5‐(4‐pyridyl)tetrazolate, py = pyridine], respectively. Complex 1 possesses two identical and independent rectangular grid sheets with twofold parallel interpenetration, in which the four‐connected nodes of the net are provided by Zn 2 (OH) units connected to one another through 4‐ptz and (4‐ptz) 2 bridges. These composite sheets are stacked one on top of another by hydrogen‐bonding interactions to afford a 3D structure. There are many structural similarities between complex 1 and the recently reported 2D layered network [Zn(OH)(4‐ptz)(H 2 O)] ( 2 ), in particular the components of the network, the coordination mode of the 4‐ptz ligand and the in situ formation of hydroxy groups. Complex 2 can be synthesized by the hydrothermal reaction of Zn(ClO 4 ) 2 ·6H 2 O and 5‐(4‐pyridyl)tetrazole in an ethanol/water/pyridine medium. The structural characterization of complex 3 shows a porous structure that contains the guest pyridine molecules. Additionally, compounds 1 and 2 exhibit strong fluorescence at room temperature in the solid state. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)