Propylated cyclotriveratrylene (CTV) ligands display different coordination chemistry over their methylated congeners as a result of increased solubility, an affinity for alkyl chain aggregation and steric factors. The propylated ligand tris(isonicotinoyl)-tris(propoxy)-cyclotricatechylene (L1p) forms a 1D coordination polymer within complex {[Ag(L1p)[Co(C2B 9H11)2]](DMF)}∞ (complex 1p), and a 2D sheet of 4·82 topology in {[Cd(L1p)(ONO 2)2(H2O)]·(DMF)·0.5(Et 2O)}∞ (complex 2p), neither of which are formed with the analogous methylated ligand tris(isonicotinoyl)-cyclotriguaiacylene (L1m). Both complexes 1p and 2p display multiple sites of aggregation of hydrophobic groups. The new propylated ligand tris(2-quinolylmethyl)-tris(propoxy)- cyclotricatechylene (L2p) forms a 1D coordination polymer with Ag(i) in complex{[Ag2(L2p)2][Co(C2B9H 11)2]2·1.5(MeNO2)} ∞ (complex 3p) and a novel, compressed octahedral structure with palladium(ii) cations, [Pd6(L2p)4(CF 3CO2)12] (complex 4p). Neither complex was accessible with the methylated congener tris(2-quinolylmethyl)- cyclotriguaiacylene (L2m).