Supramolecular Organoplatinum(IV) Chemistry: Sequential Introduction of Amide Hydrogen Bonding Groups

The self-assembly of organoplatinum(IV) complexes to give supramolecular polymers and network materials is described, using the ligand ethyl 5′-[(ethoxycarbonyl)amino]-2,2′-bipyridine-5-carboxylate (1), which contains the EtOC(═O)NH− hydrogen bonding donor group. Ligand 1 reacts with [Pt2Me4(μ-SMe2)2] to give [PtMe2(1)] (2), which forms a supramolecular polymer in the solid state through formation of intermolecular NH···O═C hydrogen bonds with further self-assembly to a sheet structure through π-stacking. Oxidative addition of bromomethyl compounds RCH2Br to complex 2 gave the corresponding organoplatinum(IV) complexes [PtBrMe2(CH2R)(1)], in which the group R could contain a further hydrogen bonding carboxamide group, and the organoplatinum(IV) complexes with two hydrogen-bond donor groups could form either supramolecular polymers or sheet structures through hydrogen bonding. As well as the anticipated NH···O═C hydrogen bonds, some complexes formed hydrogen bonds to solvent molecules NH···O(solvent) or to...