Supramolecular Complexes Built of Octahedral [Ta6Cl12(CN)6]3−/4− Clusters and Terpyridine-Metal Complexes

Abstract

The preparation and characterization of two supramolecular complexes from octahedral [Ta 6 Cl 12 (CN) 6 ] 4-/3units and 2, 2': 6', 2''-terpyridine (Terpy) metal complexes as building blocks are reported. Single crystal analyses revealed [Mn(Terpy)] 2 [Ta 6 Cl 12 (CN) 6 ]•MeOH (1) features a neutral twodimensional (2D) framework composed of layers based on [Ta 6 Cl 12 (CN) 6 ] 4and [Mn(Terpy)] 2+ . Each layer is built of 6-connected [Ta 6 Cl 12 ] 2+ and 3-connected Mn(II) nodes bridged by cyanide ligands. The layers are held together by MeOH molecules. The layered structure is maintained after the removal of solvent molecule (MeOH) upon heating, leading to the formation of [Mn(Terpy] 2 [Ta 6 Cl 12 (CN) 6 ] (1'). In the case of using Gd 3+ , the resultant product was revealed by single-crystal analyses to be an ionic 2). 2 has a three-dimensional (3D) framework built of [Gd(Terpy)(H 2 O) 4 (DMF) 2 ] 3+ and [Ta 6 Cl 12 (CN) 6 ] 3ions connected to each other via extensive hydrogen bonds and p-p interactions between the cations, anions, and solvent molecules. Thermal stabilities of 1-2 are reported.