Btzn (1), an amine-functionalized bi(1,3,5-triazine) 4,4'-(NH(2))(2)-6,6'-(NHC(6)H(5))(2)-2,2'-(1,3,5-C(3)N(3))(2), is reported, and its coordination with Co, Ni and Cu is explored. Reactions of metal salts (2 equiv) with Btzn (1 equiv) result in dimeric species [(Btzn)Co(2)(NCS)(4)(EtOH)(2)(DMF)(2)], (2), [(Btzn)Ni(2)(η(1)-ONO(2))(2)(MeOH)(4)(DMF)(2)]·2[NO(3)], (3), [(Btzn)Cu(2)Cl(4)(DMF)(2)], (4), and [(Btzn)Cu(2)(η(2)-O(2)NO)(2)(OH(2))(2)(DMF)(2)]·2[NO(3)], (5). These complexes are the first examples of the coordination of transition metals with bi(1,3,5-triazine) ligands. Their structures display a bridging bis-bidentate coordination mode for Btzn. Variable-temperature magnetic susceptibility of the complexes reveals antiferromagnetic exchange between the spin carriers, with calculated exchange coupling values (J) of -4.7 cm(-1) for 3, -18.2 cm(-1) for 4, and -5.5 cm(-1) for 5. An in-depth evaluation of the metal geometry highlights the inefficient overlap of the magnetic d-orbitals through the bridging ligand, most likely leading to reduced delocalization and coupling.