T. V. Brinzari

Pressure-Induced Magnetic Crossover Driven by Hydrogen Bonding in CuF2(H2O)2(3-chloropyridine)

Hydrogen bonding plays a foundational role in the life, earth, and chemical sciences, with its richness and strength depending on the situation. In molecular materials, these interactions determine assembly mechanisms, control superconductivity, and even permit magnetic exchange. In spite of its long-standing importance, exquisite control of hydrogen bonding in molecule-based magnets has only been realized in limited form and remains as one of the major challenges. Here, we report the discovery that pressure can tune the dimensionality of hydrogen bonding networks in CuF2(H2O)2(3-chloropyridine) to induce magnetic switching. Specifically, we reveal how the development of exchange pathways under compression combined with an enhanced ab-plane hydrogen bonding network yields a three dimensional superexchange web between copper centers that triggers a reversible magnetic crossover. Similar pressure- and strain-driven crossover mechanisms involving coordinated motion of hydrogen bond networks may play out in other quantum magnets.

Color properties and structural phase transition in penta- and hexacoordinate isothiocyanato Ni(II) compounds.

We investigated the optical properties of (NBu(4))(3)[Ni(NCS)(5)], a pentacoordinate Ni compound, and compared the results with the more traditional hexacoordinate analogue (NEt(4))(4)[Ni(NCS)(6)]. On the basis of our complementary electronic structure calculations, the color properties of this high spin complex can be understood in terms of excitations between strongly hybridized orbitals with significant Ni d and ligand character. Variable temperature vibrational studies show mode softening with decreasing temperature and splitting near 200 K, trends that we attribute to improved low temperature intermolecular interactions and a weak structural phase transition, respectively.

Local Lattice Distortions in Mn[N(CN)2]2 under Pressure.

We combined synchrotron-based infrared spectroscopy, Raman scattering, and diamond anvil cell techniques with complementary lattice dynamics calculations to reveal local lattice distortions in Mn[N(CN)2]2 under compression. Strikingly, we found a series of transitions involving octahedral counter-rotations, changes in the local Mn environment, and deformations of the superexchange pathway. In addition to reinforcing magnetic property trends, these pressure-induced local lattice distortions may provide an avenue for the development of new functionalities.

Pressure-induced local lattice distortions in α-Co[N(CN)2]2.

This work brings together diamond anvil cell techniques, vibrational spectroscopies, and complementary lattice dynamics calculations to investigate pressure-induced local lattice distortions in α-Co[N(CN)2]2. Analysis of mode behavior and displacement patterns reveals a series of pressure-driven transitions that modify the CoN6 counter-rotations, distort the octahedra, and flatten the C-N(ax)-C linkages. These local lattice distortions may be responsible for the low temperature magnetic crossover. We also discuss prospects for negative thermal expansion and show that there is not a straightforward low pressure pathway between the pink α and blue β ambient pressure phases of Co[N(CN)2]2.

Pressure–Temperature Phase Diagram Reveals Spin–Lattice Interactions in Co[N(CN)2]2

Diamond anvil cell techniques, synchrotron-based infrared and Raman spectroscopies, and lattice dynamics calculations are combined with prior magnetic property work to reveal the pressure-temperature phase diagram of Co[N(CN)2]2. The second-order structural boundaries converge on key areas of activity involving the spin state exposing how the pressure-induced local lattice distortions trigger the ferromagnetic → antiferromagnetic transition in this quantum material.

Magnetochromic effect in multiferroic R In 1 ₋ x Mn x O 3 ( R = Tb , Dy)

We combined high field magnetization and magneto-optical spectroscopy to investigate spin-charge coupling in Mn-substituted rare-earth indium oxides of chemical formula RIn₁₋xMnxO₃ (R=Tb, Dy). The edge states, on-site Mn³⁺d to d excitations, and rare-earth f-manifold excitations all track the magnetization energy due to dominant Zeeman interactions. The field-induced modifications to the rare-earth excitations are quite large because spin-orbit coupling naturally mixes spin and charge, suggesting that the next logical step in the design strategy should be to bring spin-orbit coupling onto the trigonal bipyramidal chromophore site with a 4 or 5d center.