Following the development of the idea of octupolar molecules as nonlinear optical materials a variety of compounds have been reported. Trans-porphyrins have a great potential to self-order into octupolar symmetry. Nonlinear optical properties can be tuned by using strong donor-acceptor groups in porphyrins as well as extention of conjugation. Here we report the syntheses of trans-A2D2-porphyrins and their dimerization into cubic octupoles by lanthanides and organic bidentate ligands. Bulky groups are employed to
induce non-centrosymmetric eclipsed or staggered conformations. Effect of donor acceptor groups, dimerization conditions and crystal packing of dimers are studied.