The reaction of zinc(II) salts, isophthalic acid, and four flexible unsymmetrical bis(pyridyl) ligands, namely, N-(pyridin-2-ylmethyl)pyridin-2-amine (L1), N-(pyridin-2-ylmethyl)pyridin-3-amine (L2), N-(pyridin-4-ylmethyl)pyridin-2-amine (L3), and N-(pyridin-4-ylmethyl)pyridin-3-amine (L4), gives rise to four compounds, [Zn(ip)(L1)]n (1), [Zn(ip)(L2)]n (2), [Zn3(ip)3(L3)2]n (3), and [Zn(ip)(L4)]n (4), which have been characterized by elemental analysis, IR, TG, PL, powder and single-crystal X-ray diffraction. Adjacent four- and five-coordinated Zn(II) cations in compounds 1 and 2 are joined by the ip dianions in μ2 (κ1O:κ1O) and μ3 (κ1O:κ1O:κ1O:κ1O) modes to form single and double chains. In contrast, the ip dianions in compound 3 act in μ3 (κ1O:κ1O:κ1O:κ1O) and μ4 (κ1O:κ1O:κ1O:κ1O) modes to bridge three types of zinc(II) polyhedra (four-, five- and six-coordinated), thus generating layer motif with (4·64·8)2(42·64) topology. Compound 4 presents (4,4) layer motif which is formed by the interconnection of zinc(II) tetrahedral through μ2 (κ1O:κ1O) ip dianions and anti-L4 ligands. The four bis(pyridyl) ligands in these compounds present diverse syn- and anti-conformations, which are responsible for the diversities of supramolecular networks. Moreover, solid-state luminescent properties demonstrate that the four compounds exhibit stronger emission intensities from 383 to 527nm at room temperature.