Enhancing Magnetic Properties of Molecular Magnetic Materials: The Role of Single-Ion Anisotropy
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Considerable efforts are being devoted to designing enhanced molecular magnetic materials, in particular single molecule magnets (SMMs) that can meet the requirements for future technologies such as quantum computing and spintronics. A current trend in the field is enhancing the global anisotropy in metal complexes using single-ion anisotropy. The work in this dissertation is devoted to the synthesis and characterization of new building blocks of the highly anisotropic early transition metal ion V(III) with the aim of incorporating them into heterometallic molecular materials. The results underscore the importance of tuning the local coordination environments of metal ions in order to ensure enhanced single ion anisotropy. A family of mononuclear axially distorted vanadium (III) compounds, A[L_(3)VX_(3)] (3-9) (X = F, Cl or Br, A^(+) = Et_(4)N^(+), nBu_(4)N^(+) or PPN^(+) , L_(3) = Tp or Tp* (Tp = tris(-1-pyrazolyl)borohydride), Tp* = tris(3,5-dimethyl-1-pyrazolyl)borohydride)), and [Tp*V(DMF)_(3)](PF_(6))_(2) were studied. Replacement of the Tp ligand in 3 with the stronger π-donor Tp* results in a near doubling of the magnitude of the axial zero-field splitting parameter D_(z) (D_(z) = -16.0 cm^(-1) in 3, and -30.0 cm^(-1) in 4) as determined by magnetic measurements. Such findings support the idea that controlling the axial crystal field distortion is an excellent way to enhance single-ion anisotropy. High Field-High Frequency EPR measurements on 4 revealed an even higher D value, -40.0 cm^(-1). Interestingly, compound 4 exhibits evidence for an out-of-phase ac signal under dc field. In another effort, a new series of vanadium cyanide building blocks, PPN[V(acac)_(2)(CN)_(2)]∙PPNCl (13) (acac = acetylacetonate), A[V(L)(CN)_(2)] (A^(+) = Et_(4)N^(+), L = N,N'-Ethylenebis(salicylimine) (14), A = PPN^(+), L = N,N'-Ethylenebis(salicylimine) (15), L = N,N'-Phenylenebis(salicylimine) (16), and L = N,N'-Ethylenebis(2-methoxysalicylimine) (17)) were synthesized. Magnetic studies revealed moderate Dz values (-10.0, 5.89, 3.7, 4.05 and 4.36 cm^(-1) for 13-17 respectively). The first family of cyanide-bridged lanthanide containing molecules with a trigonal bipyramidal (TBP) geometry, (Et_(4)N)_(2)[(Re(triphos)(CN)_(3))_(2)(Ln(NO_(3))_(3))_(3)]-∙4CH_(3)CN (19-27 with Ln = La, Ce, Pr, Nd, Sm, Gd, Tb, Dy and Ho) were prepared using the [(triphos)Re(CN)_(3)]^(-) building block, results that add valuable information to our database of compounds with a TBP geometry. Magnetic studies revealed diverse magnetic responses including slow relaxation of the magnetization at zero field for 25 and 26 , an indication of SMM behavior.
SubjectSingle Molecule Magnets
Trigonal bipyramidal cages
Saber, Mohamed Rashad Mohamed (2013). Enhancing Magnetic Properties of Molecular Magnetic Materials: The Role of Single-Ion Anisotropy. Doctoral dissertation, Texas A & M University. Available electronically from