Interaction of copper(II) salts with 2,2′-dipyridylamine (1), N-cyclohexylmethyl-2,2′-dipyridylamine (2), di-2-pyridylaminomethylbenzene (3), 1,2-bis(di-2-pyridylaminomethyl)-benzene (4), 1,3-bis(di-2-pyridylaminomethyl)benzene (5), 1,4-bis(di-2-pyridylaminomethyl)benzene (6), 1,3,5-tris(di-2-pyridylaminomethyl)benzene (7) and 1,2,4,5-tetrakis(di-2-pyridylaminomethyl)benzene (8) has yielded the following complexes: [Cu(2)(μ-Cl)Cl]2, [Cu(3)(μ-Cl)Cl]2·H2O, [Cu2(4)(NO3)4], [Cu2(5)(NO3)4]·2CH3OH, [Cu2(6)(CH3OH)2(NO3)4], [Cu4(8)](NO3)4]·4H2O while complexation of palladium(II) with 1, 4, 5 and 6 gave [Pd(1)2](PF6)2·2CH3OH, [Pd2(4)Cl4], [Pd2(4)(OAc)4], [Pd2(5)Cl4], [Pd2(6)Cl4] and [Pd2(6)(OAc)4]·CH2Cl2, respectively. X-ray structures of [Cu(2)(μ-Cl)Cl]2, [Cu(3)(μ-Cl)Cl]2·2C2H5OH, [Cu2(6)(CH3OH)2(NO3)4], [Pd(1)2](PF6)2·2CH3OH, [Pd2(4)(OAc)4]·4H2O and [Pd2(6)(OAc)4]·2CH2Cl2 are reported. In part, the inherent flexibility of the respective ligands has resulted in the adoption of a diverse range of coordination geometries and lattice arrangements, with the structures of [Pd2(4)(OAc)4]·4H2O and [Pd2(6)(OAc)4]·2CH2Cl2, incorporating the isomeric ligands 4 and 6, showing some common features. Liquid–liquid (H2O/CHCl3) extraction experiments involving copper(II) and 1–3, 5, 7and 8 show that the degree of extraction depends markedly on the number of dpa-subunits (and concomitant lipophilicity) of the ligand employed with the tetrakis-dpa derivative 8 acting as the most efficient extractant of the six ligand systems investigated.