The self-assembly of macrocyclic tetranuclear 3d-4f single-molecule magnet (SMM) building blocks, [(Cu3TbIII)-Tb-II(L-Pr(NO3)(2)(H2O)]NO3 (1), with K-3[M-III(CN)(6)] linkers, where M = Fe, Cr, or Co, results in a range of discrete (monomer and dimer) and one-dimensional (1D) chain (coordination polymer) supramolecular architectures, which have been structurally and magnetically characterized. The outcome of reactions of 1 with an excess of K-3[Fe(CN)(6)] has been probed in detail. It was found to be dependent on several factors, resulting in five distinctly different compounds, all of which have the same 1:1 ratio of [Cu3Tb(L-Pr)](3+) to [Fe(CN)(6)](3-), but which differ in structural type, solvent content, and magnetic behavior. Three are discrete complexes: monomeric {[Cu3Tb(L-Pr)(H2O)(5)][Fe(CN)(6)]center dot(H2O)(3)center dot(MeCN)]} (2) and [Cu3Tb(L-Pr)Fe(CN)(6)(H2O)(4)(MeCN)]center dot(H2O)(2)center dot(MeCN) (3) plus dimeric {[Cu3Tb(L-Pr)Fe-(CN)(6)(H2O)(4)]center dot(H2O)(6.75)}(2) (4), while two are 1D chains (coordination polymers): {[Cu3Tb(L-Pr)cis-Fe-(CN)(6)(H2O)(3) (MeOH)]center dot(H2O)(3.75)center dot(MeOH)(0.75)}(n) (5) and {[Cu-3 Tb(L-Pr)trans-Fe(CN)(6)(H2O)(4)]center dot(H2O)(5)center dot(DMF)(5)]}(n) (6). When K-3[Cr(CN)(6)] or K-3[Co(CN)(6)] are used in place of K-3[Fe(CN)(6)], a discrete dimer {[Cu3Tb(L-Pr)Cr(CN)(6)(H2O)(4)]center dot(H2O)(2.75)}(2) (7) and a 1D chain coordination polymer {[Cu3Tb(L-Pr)Co(CN)(6)(H2O)(3)(MeOH)]center dot(H2O)(4)-(MeOH)}(n) (8) are obtained, respectively, which are isomorphous with 4 and 5, respectively. Magnetic studies reveal the paramagnetism of these compounds down to 1.8 K, except for 7, which displays an ordered antiferromagnetic ground state with metamagnetic behavior. The 1D-coordination polymers (5, 6, and 8) do not exhibit single-chain magnet properties, because of the very weak interbuilding block magnetic interactions. For chain 8, below 2.8 K, a clear nonzero out-of-phase signal is seen, similar to that seen for the building block 1, so the magnetism of 8 is governed by that of these SMM building blocks (1).