Two novel coordination polymers, [Zn-2(FA)(4,4'-bipy)(2)]center dot 2H(2)O (1) and Cd-2(FA)(2,2'-bipy) (2), (H(4)FA = 4,4'-(hexafluoroisopropylidene)diphthalic acid, 4,4'-bipy = 4,4'-bipyridine, 2,2'-bipy = 2,2'-bipyridine), have been synthesized under hydrothermal conditions, and their structures were determined by single-crystal X-ray diffraction. Polymer 1 features an unusual three-dimensional (30) network with (4.6(2).8(3))(4(2).6(2).8(2)) topology. Polymer 2 has a complicated 31) framework and crystallizes in non-centrosymmetric space group (Fdd2) belonging to polar point group (C-2v), which displays a strong SHG response and ferroelectric properties. Moreover, the luminescent properties of 1 and 2 have also been investigated. (C) 2009 Elsevier B.V. All rights reserved.