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Seven new-type pentabasic heteropoly complexes with the general molecular formula K10 H5 [ Ln (PMo5W4V2O39)2]·nH2O(Ln = La, Ce, Pr, Nd, Eu, Gd, Dy) were synthesized. The results of IR, UV, ^31P,^51V NMR and X-ray powder diffraction pattern demonstrat