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. ; Bianca Antonioli, David J. Bray, Jack K. Clegg, Kerstin Gloe, Karsten Gloe, Anne Jäger, Katrina A. Jolliffe, Olga Kataeva, Leonard F. Lindoy, Peter J. Steel, Christopher J. Sumby and Marco Wenzel