Ln 12 ‐Containing 60‐Tungstogermanates: Synthesis, Structure, Luminescence, and Magnetic Studies

A new class of hexameric Ln 12 ‐containing 60‐tungstogermanates, [Na(H 2 O) 6 ⊂Eu 12 (OH) 12 (H 2 O) 18 Ge 2 (GeW 10 O 38 ) 6 ] 39− ( Eu 12 ), [Na(H 2 O) 6 ⊂Gd 12 (OH) 6 (H 2 O) 24 Ge(GeW 10 O 38 ) 6 ] 37− ( Gd 12 ), and [(H 2 O) 6 ⊂Dy 12 (H 2 O) 24 (GeW 10 O 38 ) 6 ] 36− ( Dy 12 ), comprising six di‐Ln‐embedded {β(4,11)‐GeW 10 } subunits was prepared by reaction of [α‐GeW 9 O 34 ] 10− with Ln III ions in weakly acidic (pH 5) aqueous medium. Depending on the size of the Ln III ion, the assemblies feature selective capture of two (for Eu 12 ), one (for Gd 12 ), or zero (for Dy 12 ) extra Ge IV ions. The selective encapsulation of a cationic sodium hexaaqua complex [Na(H 2 O) 6 ] + was observed for Eu 12 and Gd 12 , whereas Dy 12 incorporates a neutral, distorted‐octahedral (H 2 O) 6 cluster. The three compounds were characterized by single‐crystal XRD, ESI‐MS, photoluminescence, and magnetic studies. Dy 12 was shown to be a single‐molecule magnet.