Divalent metal coordination polymers containing terephthalate (tere) and bis(4-pyridylformyl)piperazine (bpfp) show diverse and interesting two-dimensional (2D) interpenetrated, three dimensional (3D) self penetrated, or one-dimensional (1D) polyrotaxane topological features. Isostructural {[M(tere)(bpfp)(H2O)(2)]center dot 4H(2)O}(n) phases (1, Zn; 2, Co) exhibit mutually inclined 2D + 2D -> 3D interpenetration of gridlike layers. {[Cd-4(tere)(4)(bpfp)(3)(H2O)(2)]center dot 8H(2)O}(n) (3) possesses a novel 3,4,8-connected trinodal self-penetrated network with (4.6(2))(2)(4(2)6(16)8(7)10(3))(4(2)6(4))(2), topology. [Zn2Cl2(tere)(bpfp)(2)](n) (4) is the first example of a 1D + 1D -> 1D polyrotaxane coordination polymer, to the best of our knowledge. Metal coordination geometry plays a crucial role in dictating the overall dimensionality in this system. Thermal decomposition behavior and luminescent properties of the d(10) configuration metal derivatives are also presented herein.