A phosphorus supported multisite coordinating ligand P(S)[N(Me)N=CH-C6H4-o-OH](3) (2) was prepared by the condensation of the phosphorus tris hydrazide P(S)[N(Me)NH2](3) (1) with o-hydroxybenzaldehyde. The reaction of 2 with M(OAc)(2).xH(2)O (M = Mn, Co, Ni, x = 4; M = Zn, x = 2) afforded neutral trinuclear complexes {P(S)[N(Me)N=CH-C6H4-o-O](3)}(2)M-3 [M = Mn (3), Co (4), Ni (5), and Zn (6)]. The X-ray crystal structures of compounds 2-6 have been determined. The structures of 3-6 reveal that the trinculear metal assemblies are nearly linear. The two terminal metal ions in a given assembly have an N3O3 ligand environment in a distorted octahedral geometry while the central metal ion has an 06 ligand environment also in a slightly distorted octahedral geometry. In all the complexes, ligand 2 coordinates to the metal ions through three imino nitrogens and three phenolate oxygens; the latter act as bridging ligands to connect the terminal and central metal ions. The compounds 2-6 also show intermolecular C-H...S=P contacts in the solid-state which lead to the formation of polymeric supramolecular architectures. The observed magnetic data for the (S = 5/2)(3) L-2(Mn(II))(3) derivative, 3, show an antiferromagnetic nearest- and next-nearest-neighbor exchange (J = -4.0 K and J' = -0.15 K; using the spin Hamiltonian (H) over cap (HDvV) = -2J((S) over cap (1)(S) over cap (2) + (S) over cap (2)(S) over cap (3)) - 2J'(S) over cap (1)(S) over cap (3)). In contrast, the (s = 1)(3) L-2(Ni(II))(3) derivative, 5, displays ferromagnetic nearest-neighbor and antiferromagnetic next-nearest-neighbor exchange interactions (J = 4.43 K and J = -0.28 K; (H) over cap= (H) over cap (HDvV) + (S) over cap D-1 (S) over cap (1) + (S) over cap D-2 (S) over cap (2) + (S) over cap D-3 (S) over cap (3)). The magnetic behavior of the L-2(Co(II))(3) derivative, 4, reveals only antiferromagnetic exchange analogous to 3 (J = -4.5, J' = -1.4; same Hamiltonian as for 3).