Polytopic alkoxy-diazine ligands with contiguous coordination pockets, self assemble in high yield to produce [2x2] M-4 grids, M-5 trigonal-bipyramidal clusters, and [3x3] M-9 grids, with alkoxide bridges between the metal centers. Large M-O-M bridge angles lead to antiferromagnetic exchange in all cases except copper, where magnetic orbital orthogonality leads to dominant ferromagnetic exchange.