Large hexadecametallic {MnIII-LnIII} wheels: synthesis, structural, magnetic, and theoretical characterization

Kuduva R Vignesh, Stuart Langley, Boujemaa Moubaraki, Keith Spencer Murray, Gopalan Rajaraman

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The synthesis, gas sorption studies, magnetic properties, and theoretical studies of new molecular wheels of core type {MnIII8LnIII8} (Ln=Dy, Ho, Er, Y and Yb), using the ligand mdeaH2, in the presence of ortho-toluic or benzoic acid are reported. From the seven wheels studied the {Mn8Dy8} and {Mn8Y8} analogues exhibit SMM behavior as determined from ac susceptibility experiments in a zero static magnetic field. From DFT calculations a S=16 ground state was determined for the {Mn8Y8} complex due to weak ferromagnetic MnIII–MnIII interactions. Ab initio CASSCF+RASSI-SO calculations on the {Mn8Dy8} wheel estimated the MnIII–DyIII exchange interaction as −0.1 cm−1. This weak exchange along with unfavorable single-ion anisotropy of DyIII/MnIII ions, however, led to the observation of SMM behavior with fast magnetic relaxation. The orientation of the g-anisotropy of the DyIII ions is found to be perpendicular to the plane of the wheel and this suggests the possibility of toroidal magnetic moments in the cluster. The {Mn8Ln8} clusters reported here are the largest heterometallic MnIIILnIII wheels and the largest {3d–4f} wheels to exhibit SMM behavior reported to date
Original languageEnglish
Pages (from-to)16364-16369
Number of pages6
JournalChemistry - A European Journal
Issue number46
Publication statusPublished - 2015


  • ab initio calculations
  • exchange-coupling
  • Mn–Ln clusters
  • single-molecule magnets
  • wheel-shaped molecule

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