[Mn 14 ] “Structural Analogues” of Well‐Known [Mn 12 ] Single‐Molecule Magnets

A new family of tetradecanuclear Mn clusters [Mn III 10 Mn IV 4 (µ 3 ‐O) 12 (EtCO 2 ) 12 (pd) 4 (EtOH) 4 (py) 4 ](ClO 4 ) 2 ( 1 ), [Mn III 10 Mn IV 4 (µ 3 ‐O) 12 (EtCO 2 ) 12 (mpd) 4 (EtOH) 2 (H 2 O) 2 (py) 4 ](ClO 4 ) 2 ( 2 ), and [Mn III 10 Mn IV 4 (µ 3 ‐O) 12 (MeCO 2 ) 10 (pic) 4 (pd) 4 (pdH 2 ) 4 ] [ 3 ] (picH = picolinic acid) were prepared from the use of the aliphatic diols 1,3‐propanediol (pdH 2 ) and 2‐methyl‐1,3‐propanediol (mpdH 2 ). The [Mn III 10 Mn IV 4 ] aggregates consist of a [Mn III 10 ] outer ring surrounding a [Mn IV 4 ] defective dicubane. Interestingly, the core of 1 – 3 is similar to those of a [Mn 12 (µ 3 ‐O) 12 (RCO 2 ) 16 (H 2 O) 4 ] “normal [Mn 12 ]” and a modified [Mn 12 ] aggregate consisting of a [Mn III 8 ] ring, surrounding a [Mn IV 4 ] defective dicubane called “flat [Mn 12 ]”. Dc and ac magnetic susceptibility studies revealed the presence of dominant antiferromagnetic exchange interactions in complexes 1 – 3 leading to small spin ground‐state values.