ABSTRACT
Synthetic control of the crystal field has elevated lanthanides to the forefront of single-molecule magnet (SMM) research, yet the resultant strong, predictable single-ion anisotropy has thus far not translated into equally impressive molecule-based magnets of higher dimensionality. This roadblock arises from the dual demands made of the crystal field: generate anisotropy and facilitate magnetic coupling. Here we demonstrate that particular metal-ligand pairs can dominate the single-ion electronic structure so fully that the remaining coordination sphere plays a minimal role in the magnitude and orientation of the magnetic anisotropy. This Metal-Ligand Pair Anisotropy (MLPA) effectively separates the crystal field into discrete components dedicated to anisotropy and magnetic coupling. To demonstrate an MLPA building unit, we synthesized four new mononuclear complexes that challenge the electronic structure of the iconic lanthanocene ([Ln(COT)2]+; COT2- = cyclooctatetraene dianion) complex which is known to generate strong anisotropy with Ln = Er3+. Variation in symmetry and coordination strength for Er(COT)I(THF)2 (THF = tetrahydrofuran) (1), Er(COT)I(Py)2 (Py = pyridine) (2), Er(COT)I(MeCN)2 (MeCN = acetonitrile) (3), and Er(COT)(Tp*) (Tp* = tris(3,5-dimethyl-1-pyrazolyl)borate) (4) shows that the Er-COT unit stabilizes anisotropy despite deliberate de-optimization. All four half-sandwich complexes display SMM behavior with effective energy barriers of U eff = 95.6(9), 102.9(3.1), 107.1(1.3), and 133.6(2.2) cm-1 for 1-4 by a multi-relaxation-process fitting. More importantly, the basic state splittings remain intact and the anisotropy axes are within several degrees of normal to the COT2- ring according to complete active space self-consistent field (CASSCF) calculations. Further investigation of the MLPA conceptual framework is warranted as it can provide building units with well-defined magnetic orientation and strength. We envision that the through-barrier processes observed herein, such as quantum tunneling, can be mitigated by formation of larger clusters and molecule-based materials.
ABSTRACT
We present the first ferromagnetically-coupled Er3+ complex with linked, high-anisotropy Er-COT (COT2- = cyclooctatetraene dianion) subunits. The dinuclear complex, [Er(µ2-Cl)(COT)(THF)]2, demonstrates single-molecule magnetism with a single, zero-field magnetization relaxation barrier of Ueff = 113 cm-1. This system offers evidence that anisotropy can be preserved in the presence of ferromagnetic linking of the Er-COT subunits, providing a rational means to build strong molecular magnets of tunable dimensionality.
ABSTRACT
The objective of this study was to develop an efficient "real time" measurement system able to directly measure, with microgram resolution, the dissolution rate of absorbable glass fibers, and utilize the system to evaluate the effectiveness of silane-based sizing as a means to delay the fiber dissolution process. The absorbable glass fiber used was calcium phosphate (CaP), with tetramethoxysilane selected as the sizing agent. E-glass fiber was used as a relatively nondegrading control. Both the unsized-CaP and sized-CaP degraded linearly at both the 37 degrees C and 60 degrees C test temperature levels used. No significant decrease in weight-loss rate was recorded when the CaP fiber tows were pretreated, using conventional application methods, with the tetramethoxysilane sizing for either temperature condition. The unsized-CaP and sized-CaP weight loss rates were each significantly higher at 60 than at 37 degrees C (both p < 0.02), as expected from dissolution kinetics. In terms of actual weight loss rate measured using our system for phosphate glass fiber, the unsized-CaP fiber we studied dissolved at a rate of 10.90 x 10(-09) and 41.20 x 10(-09) g/min-cm(2) at 37 degrees C and 60 degrees C, respectively. Considering performance validation of the developed system, the slope of the weight loss vs. time plot for the tested E-glass fiber was not significantly different compared to a slope equal to zero for both test temperatures.
