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Three novel polyoxovanadoborates namely [V 12 B 18 O 46 (OH) 14 (H 2 O) 0.75 ]·20.5H 2 O 1, Na 2 [V 12 B 18 O 48 (OH) 12 (H 2 O) 0.5 ]·26.5H 2 O 2 and Cd 0.5 {[Na(H 2 O) 2 ]2[Na(H 2 O)] 2 [Na(H 2 O) 3 ]2V 12 B 18 O 53 (OH) 7 (H 2 O) 0.5 }·11H 2 O 3 have been hydrothermally synthesized and structurally characterized. The boratopolyoxovanadate cage [V 12 B 18 O 60 ] backbones in 1-3 are constructed by the combination of two hexameric oxovanadate units [V 6 O 9 ] and one puckered [B 18 O 42 ] ring via sharing O atoms. All three compounds were obtained under alkaline conditions, and the cluster anions were all [V 12 B 18 O 60 ]. But the cations were different, it is inferred that the protonation of the three compound cluster ions is different, respectively [V 12 B 18 O 46 (OH) 14 (H 2 O) 0.75 ] in 1, [V 12 B 18 O 48 (OH) 12 (H 2 O) 0.5 ] 2 - in 2 and [V 12 B 18 O 53 (OH) 7 (H 2 O) 0.5 ] 7 - in 3. The V oxidation states ratio of V IV to V V 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 V IV . (2) Certain quasi-aromaticity from B 3 O 3 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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2019 Elsevier B.V. All rights reserved.)