Two new compounds, [Ph3PCH2Ph](2)[Zn-3(tP)(3)CL2] (1) and Ni-3(tma)(2)(H2O)(8) (2) (tp = terephthalate, tma = trimesate), are metal-polycarboxylate coordination polymers prepared by similar hydrothermal synthesis techniques. X-ray single-crystal structural analysis shows that both compounds crystallize in the 2D claylike lamellar architectures, in which 1 possesses the interlayer [Ph3PCH2Ph](+) exchangeable cation and has been confirmed by PXRD patterns. 1 (C74H56Cl2O12P2Zn3) belongs to monoclinic P2(1)/c, Z = 2 (a = 18.956(1) angstrom, b = 10.2697(5) angstrom, c = 17.067(1) angstrom, beta = 99.486(4)degrees). 2 (C18H22O20Ni3) is attributed to triclinic P (1) over bar, Z = 1 (a = 6.6643(8) angstrom, b = 9.622(1) angstrom, c = 10.089(1) angstrom, alpha = 112.675(2)degrees, beta= 94,007(1)degrees, gamma = 106.411(2)degrees). Linear metal trinuclear clusters bridged by rigid linear tp ligands for 1 and trigonal tma ligands for 2 give rise to a novel 2D 6-linked (3,6) topological anionic network in 1 and an interesting 2D 3,6-linked molybdenite topological neutral network in 2, respectively. Both compounds exhibit intense fluorescent emission bands at 410 nm (lambda(exc) = 355 nm) for 1 and 398 nrn (lambda(exc) = 300 nm) for 2 in the solid state at room temperature.