The carbophosphazene and cyclophosphazene hydrazides, [{NC(N(CH3)(2))}(2){NP{N(CH3)NH2}(2)}] (1) and [N3P3(O2C12H8)(2){N(CH3)NH2}(2)] were condensed with o-vanillin to afford the multisite coordination ligands [{NC(N(CH3)(2))}(2){NP{N(CH3)N=CH-C6H3-(o-OH)(m-OCH3)}(2)}] (2) and [{N2P2(O2C12H8)(2)}{NP{N(CH3)N=CH-C6H3-(o-OH)(m-OCH3)}(2)}] (3), respectively. These ligands were used for the preparation of heterometallic complexes [{NC(N(CH3)(2))}(2){NP{N(CH3)N=CH-C6H3-(o-O)(m-OCH3)}(2)}{CuCa(NO3)(2)}] (4), [{NC(N(CH3)(2))}(2){NP{N(CH3)N=CH-C6H3-(o-O)(m-OCH3)}(2)}{Cu2Ca2(NO3)(4) }]center dot 4H(2)O (5), [{NC(N(CH3)(2))}(2){NP{N(CH3)N=CH-C6H3-(o-O)(m-OCH3)}(2)} {CuDy(NO3)(4)}]center dot CH3COCH3 (6), [{NP(O2C12H8)}(2){NP{N(CH3)N=CH-C6H3-(o-O)(m-OCH3)}(2)}{CuDy(NO3)(3)}] (7), and [{NP(O2C12H8)}(2){NP{N(CH3)N=CH-C6H3-(o-O)(m-OCH3)}(2)}{CuTb(NO3)(3)}] (8). The molecular structures of these compounds reveals that the ligands 2, and 3 possess dual coordination pockets which are used to specifically bind the transition metal ion and the alkaline earth/lanthanide metal ion; the Cu2+/Ca2+, Cu2+/Tb3+, and Cu2+/Dy3+ pairs in these compounds are brought together by phenoxide and methoxy oxygen atoms. While 4, 6, 7, and 8 are dinuclear complexes, 5 is a tetranuclear complex. Detailed magnetic properties on 6-8 reveal that these compounds show weak couplings between the magnetic centers and magnetic anisotropy. However, the ac susceptibility experiments did not reveal any out of phase signal suggesting that in these compounds slow relaxation of magnetization is absent above 1.8 K