Two　Polyoxometalates　have　been　constructed　by　simple　hydrothermal　synthesis　using　rare-earth　(RE)　and　antimonotungstates　(ATs)　{B-α-SbW9O33}　as　raw　materials　with　the　molecular　formulas　of　H4.5Na1.5(H2O)6(C3H5N2)3{Na(Sb3O)2[B-β-SbW8O31Dy(H2O)2]3}·12H2O　(1)　and　H9(C3H5N2)5{[Sb6IIISbVDy2WO10(H2O)5][(B-β-SbW9O33)2(B-α-SbW9O33)]}·16H2O　(2).　X-ray　Single　crystal　diffractometer　analysis　shows　that　both　1　and　2　possess　trimer　configurations.　Polyoxoanion　1　is　assembled　from　three　trilacunary　{B-β-SbW8O31Dy(H2O)2}p　units　linked　via　{Na(Sb3O)2}　cluster,　where　the　trilacunary　{B-β-SbW8O31Dy(H2O)2}　unit　is　formed　by　the　tetralacunary　{B-β-SbW8O31}　unit　captures　one　Dy(H2O)23+　cation.　Polyoxoanion　2　is　composed　of　a　novel　5p−4f　heterometallic　cluster　{Sb6IIISbVDy2WO12(H2O)5}　simultaneously　stabilized　by　two　{B-β-SbW9O33}　units　and　one　{B-α-SbW9O33}　unit.　In　addition,　two-dimensional　correlation　infrared　spectroscopy　(2D　COS-IR)　under　magnetic　disturbance　was　measured　to　investigate　the　difference　of　the　variable　temperature　magnetic　susceptibility　between　two　compounds　to　explore　the　source　of　magnetic　properties,　and　further　magnetic　property　tests　indicate　that　1　and　2　may　exhibit　single-molecule-magnet　behavior　with　distinct　frequency　dependence.　This　work　deepens　the　theory　of　2D　COS-IR　and　also　enriches　the　theoretical　and　experimental　data　of　magnetism.　©　2024　Elsevier　B.V.