Synthesis of the 2,2′-dipyridylamine derivatives di-2-pyridylaminomethylbenzene , 1,2-bis(di-2-pyridylaminomethyl)benzene , 1,3-bis(di-2-pyridylaminomethyl)benzene , 2,6-bis(di-2-pyridylaminomethyl)pyridine , 1,4-bis(di-2-pyridylaminomethyl)benzene , and 1,3,5-tris(di-2-pyridylaminomethyl)benzene are reported together with the single-crystal X-ray structures of , , and . Reaction of individual salts of the type AgX (where X = NO, PF, ClO, or BF) with the above ligands has led to the isolation of thirteen Ag() complexes, nine of which have also been characterised by X-ray diffraction. In part, the inherent flexibility of the respective ligands has resulted in the adoption of a range of coordination arrangements. A series of liquid–liquid (HO/CHCl) extraction experiments of Ag() with varying concentrations of in the organic phase have been undertaken, with the counter ion in the aqueous phase being respectively picrate, perchlorate and nitrate. In general, extraction efficiencies for a given ionophore followed the Hofmeister order of picrate > perchlorate > nitrate; in each case the tris-dpa derivative acting as the most efficient extractant of the six systems investigated. Competitive seven-metal bulk membrane transport experiments (HO/CHCl/HO) employing the above ligands as the ionophore in the organic phase and equimolar concentrations of Co(), Ni(), Zn(), Cu(), Cd(), Pb() and Ag() in the aqueous source phase were also undertaken, with transport occurring against a pH gradient. Under the conditions employed and yielded negligible transport of any of the metals present in the source phase while sole transport selectivity for Ag() was observed for and .