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A synthetic procedure is presented to construct new magnetic polyoxometalates (POMs) containing one or two subunits of ‘[Co III Co3    II(OH) 3 (H 2 O) 6−m (PW 9 O 34 )] 3− ' ( m  = 3 or 5). The substitution of the water ligands present in these subunits by oxo or hydroxo ligands belonging to other POM fragments, gives rise to four, larger POM anions: [Co 7 (OH) 6 (H 2 O) 6 (PW 9 O 34 ) 2 ] 9−  ( 2 ), [Co 7 (OH) 6 (H 2 O) 4 (PW 9 O 34 ) 2 ]n    9  n  -( 2 ′), [Co 11 (OH) 5 (H 2 O) 5 (W 6 O 24 )(PW 9 O 34 ) 3 ] 22−  ( 3 ) and [{Co 4 (OH) 3 (H 2 O)(PW 9 O 34 )} 2 {K⊂(H 2 W 12 O 41 ) 2 }{Co(H 2 O) 4 } 2 ] 17−  ( 4 ). The crystal structures, magnetic characterization and stabilities in aqueous solutions of these POM derivatives are also presented.

Large Magnetic Polyoxometalates Containing the Cobalt Cubane ‘[CoIIICo3II(OH)3(H2O)6–m(PW9O34)]3−' (m = 3 or 5) as a Subunit