Designing Quantum Spaces of Higher Dimensionality from a Tetranuclear Erbium-Based Single-Molecule Magnet.

The spin relaxation of an Er3+ tetranuclear single-molecule magnet, [Er(hdcCOT)I]4, (hdcCOT = hexahydrodicyclopentacyclooctatetraenide dianion), is modeled as a near-tetrahedral arrangement of Ising-type spins. Combining evidence from single-crystal X-ray diffraction, magnetometry, and computational techniques, the slow spin relaxation is interpreted as a consequence of symmetry restrictions imposed on quantum tunneling within the cluster core. The union of spin and spatial symmetries describe a ground state spin-spin coupled manifold wherein 16 eigenvectors generate the 3D quantum spin-space described by the vertices of a rhombic dodecahedron. Analysis of the experimental findings in this context reveals a correlation between the magnetic transitions and edges connecting cubic and octahedral subsets of the eigenspace convex hull. Additionally, the model is shown to map to a theoretically proposed quantum Cayley network, indicating an underexplored synergy between mathematical descriptions of molecular spin interactions and quantum computing configuration spaces

Coordination chemistry in molecular symmetry adapted spin space (mSASS)

Many areas of chemistry are devoted to the challenge of understanding, predicting, and controlling the behavior of strongly localized electrons. Examples include molecular magnetism and luminescence, color centers in crystals, photochemistry and quantum sensing to name but a few. Over the years, an amalgam of powerful quantum chemistry methods, simple intuitive models, and phenomenological parameterizations have been developed, providing increasingly complex and specialized methodologies. Even with increasing specialization, a pervasive challenge remains that is surprisingly universal - the simultaneous description of continuous symmetries (e.g. spin and orbital angular momenta) and discrete symmetries (e.g. crystal field). Modeling behavior in these complex systems is increasingly important for metal ions of unusual or technologically relevant behavior. Additionally, development of broad-scope models with physically-meaningful parameters carries the potential to facilitate interdisciplinary collaboration and large-scale meta analysis. We propose a generalized algorithmic approach, the molecular symmetry adapted spin space (mSASS), to localized electronic structure. We derive the Hamiltonian in symmetry-constrained matrix form with an exact account of free parameters and examples. Although preliminary in its implementation, a fundamental benefit of this approach is the treatment of spatial and spin-orbit symmetries without the need for perturbative approximations. In general, the mSASS Hamiltonian is large but finite and can be diagonalized numerically with high efficiency, providing a basis for conceptual models of electronic structure that naturally incorporates spin while leveraging the intuition and efficiency benefits of crystallographic symmetry. For the generation of the mSASS Hamiltonian, we provide an implementation into the Mathematica Software Package, GTPack.Comment: 10 pages, 4 figure

Coastal Development, Environmental Amenities, and Market Forces: An Application of Economic Theory

James R. Rinehart, Ph.D., is professor of economics, Francis Marion University, Florence, SC 29501. Jeffrey J. Pompe, Ph.D., is associate professor of economics, Francis Marion University, Florence, SC 29501

The Effect of Golf Course Location on Housing Value

Structural and locational characteristics are known to affect housing prices, and numerous studies have explored many of these characteristics. However very little empirical information was available on the effect of golf course location for improved property. Two recent studies find that building on a golf course adds 7 to 8 percent to the value of property. However, we find that for a private development on a barrier island, building a villa or single family home on a golf course does not have any significant impact on price. Specific locational factors may explain this unexpected result

Slow magnetic relaxation in homoleptic trispyrazolylborate complexes of neodymium(iii) and uranium(iii)

Lanthanide- and actinide-based single-molecule magnets are rapidly gaining prominence due to the unique properties of f-orbitals, yet no direct comparison of slow magnetic relaxation of an isostructural and valence isoelectronic lanthanide and actinide complex exists. We present the dynamic magnetic properties of two f-element single-molecule magnets, NdTp(3) and UTp(3) (Tp(-) = trispyrazolylborate), demonstrating that, although neither complex displays the full anisotropy barrier predicted from its electronic structure, relaxation is slower in the uranium congener. Magnetic dilution studies performed with NdTp(3) reveal that, while intermolecular interactions partially account for the faster relaxation dynamics, they are not uniquely responsible

Strong exchange and magnetic blocking in N 2 32 -radical-bridged lanthanide complexes

Single-molecule magnets approach the ultimate size limit for spin-based devices. These complexes can retain spin information over long periods of time at low temperature, suggesting possible applications in high-density information storage, quantum computing and spintronics. Notably, the success of most such applications hinges upon raising the inherent molecular spin-inversion barrier. Although recent advances have shown the viability of lanthanide-containing complexes in generating large barriers, weak or non-existent magnetic exchange coupling allows fast relaxation pathways that mitigate the full potential of these species. Here, we show that the diffuse spin of an N 2 32 radical bridge can lead to exceptionally strong magnetic exchange in dinuclear Ln(III) (Ln 5 Gd, Dy) complexes. The Gd(III) congener exhibits the strongest magnetic coupling yet observed for that ion, while incorporation of the high-anisotropy Dy(III) ion gives rise to a molecule with a record magnetic blocking temperature of 8.3 K at a sweep rate of 0.08 T s 21

High Relaxivity Gadolinium-Polydopamine Nanoparticles

AbstractThis study reports the preparation of a series of gadolinium‐polydopamine nanoparticles (GdPD‐NPs) with tunable metal loadings. GdPD‐NPs are analyzed by nuclear magnetic relaxation dispersion and with a 7‐tesla (T) magnetic resonance imaging (MRI) scanner. A relaxivity of 75 and 10.3 mM−1 s−1 at 1.4 and 7 T is observed, respectively. Furthermore, superconducting quantum interference device magnetometry is used to study intraparticle magnetic interactions and determine the GdPD‐NPs consist of isolated metal ions even at maximum metal loadings. From these data, it is concluded that the observed high relaxivities arise from a high hydration state of the Gd(III) at the particle surface, fast rate of water exchange, and negligible antiferromagnetic coupling between Gd(III) centers throughout the particles. This study highlights design parameters and a robust synthetic approach that aid in the development of this scaffold for T1‐weighted, high relaxivity MRI contrast agents

Structure and Function of Iron-Loaded Synthetic Melanin

We describe a synthetic method for increasing and controlling the iron loading of synthetic melanin nanoparticles and use the resulting materials to perform a systematic quantitative investigation on their structure 12property relationship. A comprehensive analysis by magnetometry, electron paramagnetic resonance, and nuclear magnetic relaxation dispersion reveals the complexities of their magnetic behavior and how these intraparticle magnetic interactions manifest in useful material properties such as their performance as MRI contrast agents. This analysis allows predictions of the optimal iron loading through a quantitative modeling of antiferromagnetic coupling that arises from proximal iron ions. This study provides a detailed understanding of this complex class of synthetic biomaterials and gives insight into interactions and structures prevalent in naturally occurring melanins

Size-Controlled Hapticity Switching in [Ln(C9H9)(C8H8)][Ln(C_{9}H_{9})(C_{8}H_{8})] Sandwiches

Sandwich complexes of lanthanides have recently attracted a considerable amount of interest due to their applications as Single Molecule Magnet (SMM). Herein, a comprehensive series of heteroleptic lanthanide sandwich complexes ligated by the cyclononatetraenyl (Cnt) and the cyclooctatetraenyl (Cot) ligand [Ln(Cot)(Cnt)] (Ln=Tb, Dy, Er, Ho, Yb, and Lu) is reported. The coordination behavior of the Cnt ligand has been investigated along the series and shows different coordination patterns in the solid-state depending on the size of the corresponding lanthanide ion without altering its overall anisotropy. Besides the characterization in the solid state by single-crystal X-ray diffraction and in solution by $^{1}H$NMR, static magnetic studies and ab initio computational studies were performed