Assembly of Hydrogen‐Bonded Organic Layers with Macrocyclic Complexes Acting as Pillars

Abstract

Abstract Novel supramolecular networks of 2D {[Ni(cyclam)][C 6 H 9 (COOH) 2 (COO)] 2 } n ( 1 ) and 3D {[Ni(cyclam)][C 6 H 3 (OH) 2 (COO)] 2 } n ( 2 ) have been constructed by the self‐assembly of [Ni(cyclam)](ClO 4 ) 2 with cis , cis ‐1,3,5‐cyclohexanetricarboxylic acid (H 3 CTC) and 3,5‐dihydroxybenzoic acid (HDHB), respectively, in py/MeCN/H 2 O. In the crystal structure of 1 , each nickel( II ) macrocyclic complex binds two H 2 CTC − ions at the axial sites. The coordinated H 2 CTC − ions form hydrogen bonds with one another, which results in organic bilayers having macrocyclic complexes as pillars. In the crystal structure of 2 , each nickel( II ) macrocyclic complex binds two DHB − ions in the trans position. Two free hydroxyl groups and one carbonyl oxygen atom of the coordinated DHB − ion are extensively hydrogen‐bonded with the DHB − ligand of the neighboring complexes, which results in a 3D network where 2D organic layers are linked by the macrocyclic complexes acting as pillars. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)