Supramolecular Assembly of Organophosphonate Diesters Using Paddle-Wheel Complexes: First Examples in Porphyrin Series

The reactions of dicopper tetrapivalate complex Cu2(μ-OOC-t-Bu)4(NCMe)2 (1) with triphenylphosphine oxide and diethyl phosphite allow paddle-wheel (PW) copper(II) complexes with phosphorus-containing axial ligands (2, 3) to be obtained. When meso-bis(diethoxyphosphoryl)porphyrins 4M were employed in this ligand exchange reaction, a series of one-dimensional (1D) homo- and heterometallic coordination polymers 5M composed of PW subunits and organophosphonate diesters were prepared and characterized by means of single crystal X-ray analysis. Planar porphyrinate 4Pd and nonplanar metalloporphyrinates 4Cu and 4Ni proved to be appropriate molecular structural blocks for assembly of coordination p…