Unprecedented high-nuclear transition-metal-cluster-substituted heteropolyoxoniobates: synthesis by {V8 } ring insertion into the POM matrix and antitumor activities.

Reactions of hexaniobate with vanadate in the presence of Ni(2+) , Zn(2+) , or Cu(2+) have furnished three high-nuclear vanadium cluster-substituted heteropolyoxoniobates (HPNs): {Ni(en)3 }5 H{V(V) Nb8 V(IV) 8 O44 }⋅9 H2 O (1), (H2 en)Na2 [{Zn(en)2 (Hen)}{Zn(en)2 (H2 O)}2 {PNb8 V(IV) 8 O44 }]⋅11 H2 O (2), and Na{Cu(en)2 }3 {[Cu(en)2 ]2 [PNb8 V(IV) 8 O44 ]}⋅11 H2 O (3) (en=1,2-diaminoethane). Their structures have been determined and characterized by single-crystal X-ray diffraction analysis, thermogravimetric analysis (TGA), and elemental analysis. Structural analysis has revealed that compounds 1-3 contain similar {V8 }-substituted [X(V) Nb8 V(IV) 8 O44 ](11-) (X=P, V) clusters, obtained by inserting a {V8 } ring into tetravacant HPN [XNb8 O36 ](27-) . To the best of our knowledge, compounds 1-3 represent the first high-nuclear vanadium cluster-substituted HPNs, and compound 1 is the largest vanadoniobate cluster yet obtained in HPN chemistry. Nickel and zinc cations have been introduced into HPNs for the first time, which might promise a more diverse set of structures in this family. Antitumor studies have indicated that compounds 1 and 2 exhibit high activity against human gastric cancer SGC-7901 cells, SC-1680 cells, and MG-63 cells.