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Item Direct observation of the magnetic anisotropy of an Fe(II) spin crossover molecular thin film(IOPP, 2023-07) Dale, Ashley S.; Yazdani, Saeed; Ekanayaka, Thinlini K.; Mishra, Esha; Hu, Yuchen; Dowben, Peter A.; Freeland, John W.; Zhang, Jian; Cheng, Ruihua; Physics, School of ScienceIn this work, we provide clear evidence of magnetic anisotropy in the local orbital moment of a molecular thin film based on the SCO complex [Fe(H2B(pz)2)2(bipy)] (pz = pyrazol−1−yl, bipy = 2,2'−bipyridine). Field dependent x-ray magnetic circular dichroism measurements indicate that the magnetic easy axis for the orbital moment is along the surface normal direction. Along with the presence of a critical field, our observation points to the existence of an anisotropic energy barrier in the high-spin state. The estimated nonzero coupling constant of ∼2.47 × 10−5 eV molecule−1 indicates that the observed magnetocrystalline anisotropy is mostly due to spin–orbit coupling. The spin- and orbital-component anisotropies are determined to be 30.9 and 5.04 meV molecule−1, respectively. Furthermore, the estimated g factor in the range of 2.2–2.45 is consistent with the expected values. This work has paved the way for an understanding of the spin-state-switching mechanism in the presence of magnetic perturbations.Item Magnetic Field Perturbations to a Soft X-ray-Activated Fe (II) Molecular Spin State Transition(MDPI, 2021-10) Hao, Guanhua; N’Diaye, Alpha T.; Ekanayaka, Thilini K.; Dale, Ashley S.; Jiang, Xuanyuan; Mishra, Esha; Mellinger, Corbyn; Yazdani, Saeed; Freeland, John W.; Zhang, Jian; Cheng, Ruihua; Xu, Xiaoshan; Dowben, Peter A.; Physics, School of ScienceThe X-ray-induced spin crossover transition of an Fe (II) molecular thin film in the presence and absence of a magnetic field has been investigated. The thermal activation energy barrier in the soft X-ray activation of the spin crossover transition for [Fe{H2B(pz)2}2(bipy)] molecular thin films is reduced in the presence of an applied magnetic field, as measured through X-ray absorption spectroscopy at various temperatures. The influence of a 1.8 T magnetic field is sufficient to cause deviations from the expected exponential spin state transition behavior which is measured in the field free case. We find that orbital moment diminishes with increasing temperature, relative to the spin moment in the vicinity of room temperature.Item Probing the unpaired Fe spins across the spin crossover of a coordination polymer(RSC, 2021) Ekanayaka, Thilini K.; Kurz, Hannah; Dale, Ashley S.; Hao, Guanhua; Mosey, Aaron; Mishra, Esha; N'Diaye, Alpha T.; Cheng, Ruihua; Weber, Birgit; Dowben, Peter A.; Physics, School of ScienceFor the spin crossover coordination polymer [Fe(L1)(bipy)]n (where L1 is a N2O22− coordinating Schiff base-like ligand bearing a phenazine fluorophore and bipy = 4,4′-bipyridine), there is compelling additional evidence of a spin state transition. Both Fe 2p X-ray absorption and X-ray core level photoemission spectroscopies confirm that a spin crossover takes place, as observed by magnetometry. Yet the details of the temperature dependent changes of the spin state inferred from both X-ray absorption and X-ray core level photoemission, differ from magnetometry, particularly with regard to the apparent critical transition temperatures and the cooperative nature of the curve progression in general. Comparing the experimental spin crossover data to Ising model simulations, a transition activation energy in the region of 160 to 175 meV is indicated, along with a nonzero exchange J. Overall, the implication is that there may be perturbations to the bistability of spin states, that are measurement dependent or that the surface differs from the bulk with regard to the cooperative effects observed upon spin transition.Item Quantitative Study of the Energy Changes in Voltage-Controlled Spin Crossover Molecular Thin Films(ACS, 2020-09) Mosey, Aaron; Dale, Ashley S.; Hao, Guanhua; N'Diaye, Alpha; Dowben, Peter A.; Cheng, Ruihua; Physics, School of ScienceVoltage-controlled nonvolatile isothermal spin state switching of a [Fe{H2B(pz)2}2(bipy)] (pz = tris(pyrazol-1–1y)-borohydride, bipy = 2,2′-bipyridine) film, more than 40 to 50 molecular layers thick, is possible when it is adsorbed onto a molecular ferroelectric substrate. Accompanying this high-spin and low-spin state switching, at room temperature, we observe a remarkable change in conductance, thereby allowing not only nonvolatile voltage control of the spin state (“write”) but also current sensing of the molecular spin state (“read”). Monte Carlo Ising model simulations of the high-spin state occupancy, extracted from X-ray absorption spectroscopy, indicate that the energy difference between the low-spin and high-spin state is modified by 110 meV. Transport measurements demonstrate that four terminal voltage-controlled devices can be realized using this system.