MCD spectroscopy of hexanuclear Mn(III) salicylaldoxime single-molecule magnets

Justin M. Bradley, Andrew J. Thomson, Ross Inglis, Constantinos J. Milios, Euan K. Brechin, Stergios Piligkos

Research output: Contribution to journalArticlepeer-review

Abstract

The hexanuclear cages [Mn6O2(R-sao)(6)L-2(EtOH)(x)(H2O)(y)] "Mn-6" behave as single-molecule magnets (SMMs) below a characteristic blocking temperature. As with [Mn12O12(O2CR)(16)(H2O)(4)] "Mn-12" the electronic absorption spectra are rather featureless, yielding little information on the electronic structure of the magnetic ions. Low temperature Magnetic Circular Dichroism (MCD) spectra afford greater resolution of the optical transitions and also probe the magnetic properties of the system. Both the ground state spin and blocking temperature of the Mn-6 cages are determined by subtle structural perturbations of a generic Mn6O2 core. Absorbance and MCD spectra are reported for [Mn6O2(Et-sao)(6){O2CPh(Me)(2)}(2)(EtOH)(6)] (1), [Mn6O2(Et-sao)(6){O2CPh}(2)(EtOH)(4)(H2O)(2)] (2), [Mn6O2(sao)(6){O2CPh}(2)(EtOH)(4)]center dot EtOH (3) and the trinuclear precursor [Mn3O(Et-sao)(3)(MeOH)(3)](ClO4) (4) cast into polymer film. SMM behaviour has previously been observed using magnetic susceptibility measurements on powder and single-crystal samples. The ligand field environment of the magnetic ions is assumed to be similar in (1) and (2) and their different blocking temperatures are attributed to the magnitude of the effective exchange constant. The MCD spectra of (1) and (2), in which the ground state spin S = 12, show that the ligand field environments of the Mn ions are almost identical and that magnetic hysteresis persists for isolated molecules when crystal packing forces are removed. The subtle structural differences between (1) and (2) are manifested in the field dependence of the MCD response at different wavelengths that reflect changes in band polarisation. The MCD spectrum of (3) contains features not apparent in those of (1) and (2). These are attributed to 5-coordinate Mn(III), which is unique to (3) among the compounds studied. (3) has ground state spin S = 4, a lower blocking temperature and consequently no observable hysteresis in the MCD down to 1.7 K. Comparison of the MCD spectra of (1)-(3) to that of (4) confirms the integrity of the Mn6O2 core when these materials are cast into polymer film.

Original languageEnglish
Pages (from-to)9904-9911
Number of pages8
JournalDalton Transactions
Volume39
Issue number41
DOIs
Publication statusPublished - 2010

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