Two　novel　polyoxovanadoborates　with　the　similar　vanadium　cage　but　different　number　of　ligand　have　been　hydrothermally　synthesized,　namely　(enH2)6[V12B18O58(OH)2(H2O)0.5]　12H2O　and　(enH2)10[V12B18O56(OH)4(H2O)]2　16H2O.　The　structure　of　1　and　2　was　determined　by　single　crystal　X-ray　diffraction.　Both　compounds　are　connected　to　form　a　supramolecular　structure　through　hydrogen　bonding.　But　the　number　of　free　ethylenediamine　molecules　outside　the　cage　of　the　two　compounds　is　different,　and　so　is　the　pilling　way　stacked　by　hydrogen　bonding.　We　use　two-dimensional　infrared　correlation　spectroscopy　(2D　IR　COS),　thermogravimetry　(TG),　and　high　temperature　infrared　(HTIR)　to　study　the　effect　of　hydrogen　bonding　on　the　thermal　stability　for　two　compounds.　From　the　two-dimensional　infrared　correlation　spectrum,　it　can　be　seen　that　the　response　peaks　of　νs(V-Oμ),　νas(V-Oμ),　νs(V=Ot),　νas(V=Ot),　νas(Ba–O)　and　νas(Bb-O)　of　the　two　compounds　are　different,　which　may　be　caused　by　the　different　connection　modes　between　the　weak　interaction　forces　of　the　two　compounds.　The　analysis　results　of　TG　and　HTIR　curves　are　consistent　with　the　2D　IR　COS.　Three　characterization　methods　show　that　hydrogen　bonding　can　not　only　increase　the　initial　temperature　of　organic　functional　groups　and　crystal　water　decomposition,　but　also　greatly　affect　the　temperature　at　which　cluster　cages　begin　to　decompose.　2D-IR　COS　provides　an　effective　new　method　for　studying　hydrogen　bonding.　©　2020　Elsevier　B.V.