Three　novel　polyoxovanadoborates　namely　[V12B18O46(OH)14(H2O)0.75]·20.5H2O　1,　Na2[V12B18O48(OH)12(H2O)0.5]·26.5H2O　2　and　Cd0.5{[Na(H2O)2]2[Na(H2O)]2[Na(H2O)3]2V12B18O53(OH)7(H2O)0.5}·11H2O　3　have　been　hydrothermally　synthesized　and　structurally　characterized.　The　boratopolyoxovanadate　cage　[V12B18O60]　backbones　in　1–3　are　constructed　by　the　combination　of　two　hexameric　oxovanadate　units　[V6O9]　and　one　puckered　[B18O42]　ring　via　sharing　O　atoms.　All　three　compounds　were　obtained　under　alkaline　conditions,　and　the　cluster　anions　were　all　[V12B18O60].　But　the　cations　were　different,　it　is　inferred　that　the　protonation　of　the　three　compound　cluster　ions　is　different,　respectively　[V12B18O46(OH)14(H2O)0.75]　in　1,　[V12B18O48(OH)12(H2O)0.5]2　−　in　2　and　[V12B18O53(OH)7(H2O)0.5]7　−　in　3.　The　V　oxidation　states　ratio　of　VIV　to　VV　were　2:1　confirmed　by　valence　bond　calculation　and　XPS.　We　studied　the　magnetic　properties　of　three　compounds　by　two　methods:　The　variable　temperature　magnetic　susceptibility　and　the　2D　IR　COS　under　magnetic　perturbation.　From　the　2D　IR　COS　under　magnetic　perturbation　map,　it　is　showed　that　all　three:　(1)　the　presence　of　VIV.　(2)　Certain　quasi-aromaticity　from　B3O3　six-membered　ring.　(3)　The　difference　of　protonation　and　the　charge　of　the　cluster　anions.　This　work　enriches　the　theory　of　two-dimensional　correlation　spectroscopy　and　also　provides　a　new　approach　to　the　study　of　magnetic　materials.　©　2019　Elsevier　B.V.