Zn/Mn–MOFs with `S-shaped' packing modes

Abstract

Two novel polymers exhibiting metal-organic frameworks (MOFs) have been synthesized by the combination of a metal ion with a benzene-1,3,5-tricarboxylate ligand (BTC) and 1,10-phenanthroline (phen) under hydrothermal conditions. The first compound, poly[[(μ4-benzene-1,3,5-tricarboxylato-κ(4)O:O':O'':O''')(μ-hydroxido-κ(2)O:O)bis(1,10-phenanthroline-κ(2)N,N')dizinc(II)] 0.32-hydrate], {[Zn2(C9H3O6)(OH)(C12H8N2)2]·0.32H2O}n, denoted Zn-MOF, forms a two-dimensional network in which a binuclear Zn2 cluster serves as a 3-connecting node; the BTC trianion also acts as a 3-connecting centre. The overall topology is that of a 6(3) net. The phen ligands serve as appendages to the network and interdigitate with phen ligands belonging to adjacent parallel sheets. The second compound, poly[[(μ6-benzene-1,3,5-tricarboxylato-κ(7)O(1),O(1'):O(1):O(3):O(3'):O(5):O(5'))(μ3-hydroxido-κ(2)O:O:O)(1,10-phenanthroline-κ(2)N,N')dimanganese(II)] 1.26-hydrate], {[Mn2(C9H3O6)(OH)(C12H8N2)]·1.26H2O}n, denoted Mn-MOF, exists as a three-dimensional network in which an Mn4 cluster serves as a 6-connecting unit, while the BTC trianion again plays the role of a 3-connecting centre. The overall topology is that of the rutile net. Phen ligands act as appendages to the network and form the `S-shaped' packing mode.