Comprehensive Studies of Magnetic Properties of Metal-Organic Frameworks and Molecular Compounds

Single-ion magnets (SIMs) are at the forefront of molecular electronic spin magnets with potential applications in magnetic memory storage devices. However, the magnetic properties of the SIMs are yet to be completely understood, especially the magnetic properties of large anisotropy systems. A part of this dissertation is to utilize optical and neutron spectroscopies such as far-IR magneto-spectroscopy (FIRMS) and inelastic neutron scattering (INS) to quantify the anisotropy and study the phonon properties of the SIMs as two-dimensional (2-D) metal-organic frameworks (MOFs) or coordination polymer (CP), and a molecular magnet. In addition, ab initio calculations are used to understand the origin of the anisotropy and the electronic structure of the systems. Furthermore, the systems studied in this dissertation can also be quantum bit (qubit) candidates. Qubits are the building blocks of quantum computers. The properties of qubits can be determined using pulsed electron paramagnetic resonance (pulsed EPR). The results yielded the spin-lattice relaxation time and the spin-spin relaxation time, where both relaxation times are crucial in determining the effectiveness of the qubit candidates. The second part of this dissertation focuses on studying the symmetry-protected topological states of a Haldane one-dimensional (1-D) spin-1 chain as a 2-D MOF. The topological properties of the Haldane spin-1 chain can be highlighted by the Haldane energy gap that exists between the non-magnetic singlet ground state and the triplet excited state, the fractionalized edge states, and the system’s robustness to external perturbations through symmetry-protection. Optical and neutron spectroscopies in addition to the magnetic susceptibility measurements were used to quantify the energy gaps as well as the anisotropy that governs the system. Furthermore, the spin chain is found to exhibit a critical field and critical temperature where the system observes a phase transition. These studies in this dissertation, in part, aim to give a complete understanding of the magnetic anisotropy and phonon properties of the SIM and qubit systems as well as to have a comprehensive understanding of the topological properties of the Haldane 1-D spin-1 chain system

Haldane topological spin-1 chains in a planar metal-organic framework

Abstract Haldane topological materials contain unique antiferromagnetic chains with symmetry-protected energy gaps. Such materials have potential applications in spintronics and future quantum computers. Haldane topological solids typically consist of spin-1 chains embedded in extended three-dimensional (3D) crystal structures. Here, we demonstrate that [Ni(μ−4,4′-bipyridine)(μ-oxalate)]n (NiBO) instead adopts a two-dimensional (2D) metal-organic framework (MOF) structure of Ni2+ spin-1 chains weakly linked by 4,4′-bipyridine. NiBO exhibits Haldane topological properties with a gap between the singlet ground state and the triplet excited state. The latter is split by weak axial and rhombic anisotropies. Several experimental probes, including single-crystal X-ray diffraction, variable-temperature powder neutron diffraction (VT-PND), VT inelastic neutron scattering (VT-INS), DC susceptibility and specific heat measurements, high-field electron spin resonance, and unbiased quantum Monte Carlo simulations, provide a detailed, comprehensive characterization of NiBO. Vibrational (also known as phonon) properties of NiBO have been probed by INS and density-functional theory (DFT) calculations, indicating the absence of phonons near magnetic excitations in NiBO, suppressing spin-phonon coupling. The work here demonstrates that NiBO is indeed a rare 2D-MOF Haldane topological material

Advanced Magnetic Resonance Studies of Tetraphenylporphyrinatoiron(III) Halides

High-Frequency and -Field EPR (HFEPR) studies of Fe(TPP)X (X = F, Cl, Br; I, TPP2−= meso-tetraphenylporphyrinate dianion) and far-IR magnetic spectroscopic (FIRMS) studies of Fe(TPP)Br and Fe(TPP)I have been conducted to probe magnetic intra- and inter-Kramers doublet transitions in these S = 5/2 metalloporphyrin complexes, yielding zero-field splitting (ZFS) and g parameters for the complexes: Fe(TPP)F, D =  +4.67(1) cm−1, E = 0.00(1) cm−1, g⊥ = 1.97(1), g|| = 2.000(5) by HFEPR; Fe(TPP)Cl, D =  +6.458(2) cm−1, E =  +0.015(5) cm−1, E/D = 0.002, g⊥ = 2.004(3), g|| = 2.02(1) by HFEPR; Fe(TPP)Br, D = +9.03(5) cm−1, E =  +0.047(5) cm−1, E/D = 0.005, giso = 1.99(1) by HFEPR and D = +9.05 cm−1, giso = 2.0 by FIRMS; Fe(TPP)I, D =  +13.84 cm−1, E =  +0.07 cm−1, E/D = 0.005, giso = 2.0 by HFEPR and D = +13.95 cm−1, giso = 2.0 by FIRMS (the sign of E was in each case arbitrarily assigned as that of D). These results demonstrate the complementary nature of field- and frequency-domain magnetic resonance experiments in extracting with high accuracy and precision spin Hamiltonian parameters of metal complexes with S > 1/2. The spin Hamiltonian parameters obtained from these experiments have been compared with those obtained from other physical methods such as magnetic susceptibility, magnetic Mössbauer spectroscopy, inelastic neutron scattering (INS), and variable-temperature and -field magnetic circular dichroism (VT-VH MCD) experiments. INS, Mössbauer and MCD give good agreement with the results of HFEPR/FIRMS; the others not as much. The electronic structure of Fe(TPP)X (X = F, Cl, Br, I) was studied earlier by multi-reference ab initio methods to explore the origin of the large and positive D-values, reproducing the trends of D from the experiments. In the current work, a simpler model based on Ligand Field Theory (LFT) is used to explain qualitatively the trend of increasing ZFS from X = F to Cl to Br and to I as the axial ligand. Tetragonally elongated high-spin d5 systems such as Fe(TPP)X exhibit D > 0, but X plays a key role. Spin delocalization onto X means that there is a spin–orbit coupling (SOC) contribution to D from X•, as opposed to none from closed-shell X−. Over the range X = F, Cl, Br, I, X• character increases as does the intrinsic SOC of X• so that D increases correspondingly over this range