Ferromagnetic manganese "cubes": from PSII to single-molecule magnets

Ross Inglis, Constantinos C. Stoumpos, Alessandro Prescimone, Milosz Siczek, Tadeusz Lis, Wolfgang Wernsdorfer, Euan K. Brechin, Constantinos J. Milios

Research output: Contribution to journalArticlepeer-review

Abstract

The reaction of Mn(O2CMe)(2)center dot 2H(2)O with Me-saoH(2) (Me-saoH(2) = 2-hydroxyphenylethanone oxime) in MeCN forms the complex [Mn-4(III)(Me-sao)(4)(Me-saoH)(4)] (1) in good yields. Replacing Me-saoH(2) with Naphth-saoH(2) (Naphth-saoH(2) = 2-hydroxy-1-napthaldoxime) in the presence of CH3ONa forms the complex [Mn-4(III)(Naphth-sao)(4)(Naphth-saoH)(4)] (2) in low yields, while the reaction between Mn(ClO4)(2)center dot 6H(2)O, Et-saoH(2) (Et-saoH(2) = 2-hydroxypropiophenone oxime) and NBu4OH in MeCN gives the complex [Mn-4(III)(Et-sao)(4)(Et-saoH)(4)] (3) in moderate yields. All three tetrametallic cages exclusively contain Mn-III centres arranged in a "cube"-like topology, in which the metal centres are connected by-N-O-oximate groups. The magnetic properties of 1-3 are near identical, revealing the presence of only ferromagnetic interactions between the metal ions leading to high-spin ground states of S = 8. The complexes display frequency dependent out-of-phase signals in ac susceptibility studies and, in the case of 1 single-molecule magnetism has been observed by means of single-crystal hysteresis loop measurements.

Original languageEnglish
Pages (from-to)4777-4785
Number of pages9
JournalDalton Transactions
Volume39
Issue number20
DOIs
Publication statusPublished - 2010

Keywords

  • PHOTOSYNTHETIC WATER OXIDATION
  • NEUTRON-SCATTERING SPECTRA
  • OXYGEN-EVOLVING COMPLEX
  • PHOTOSYSTEM-II
  • CRYSTAL-STRUCTURES
  • ELECTRON-TRANSFER
  • ENERGY-LEVELS
  • TETRANUCLEAR
  • TRINUCLEAR
  • CLUSTER

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