A cascade approach to hetero-pentanuclear manganese-oxide clusters in polyoxometalates and their single-molecule magnet propertiesElectronic supplementary information (ESI) available: Experimental details including syntheses, crystallographic data, IR and CSI-MS spectra, and magnetic data. CCDC 1049411-1049419. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5dt01363a

• Main Authors: Suzuki, Kosuke, Sato, Rinta, Minato, Takuo, Shinoe, Masahiro, Yamaguchi, Kazuya, Mizuno, Noritaka
• Format: Article
• Language: English
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/c5dt01363a

Structurally well-defined hetero-pentanuclear manganese-oxide clusters {MMn 4 } were successfully synthesized in TBA 7 H n [MMn 4 (OH) 2 (A-α-SiW 9 O 34 ) 2 ]·2H 2 O·C 2 H 4 Cl 2 ( II MMn4 , M = Fe( iii ), Co( ii ), Ni( ii ), Cu( ii ), Ga( iii )) by sequential introduction of metal cations into the trivacant lacunary polyoxometalates (POMs). The pentanuclear manganese-oxide cluster {Mn 5 } showed a small spin ground state and a low energy barrier for magnetization relaxation. In contrast, the magnetic interactions in the hetero-pentanuclear clusters could be controlled by the arrangements of metals, and the clusters showed large magnetic anisotropy and single-molecule magnet behavior. In particular, the cluster {FeMn 4 } in II FeMn4 ( S = 11/2) showed the slowest relaxation and the highest energy barrier among the previously reported transition metal-containing POMs. Hetero-pentanuclear clusters {MMn 4 } with large uniaxial magnetic anisotropy and SMM behavior were successfully synthesized by sequential introduction of metal cations into the trivacant lacunary polyoxometalates.