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A collection of studies are reported that focus on the examination of exchange interactions in complexes containing paramagnetic ions with a large magnetic anisotropy. A number of complementary techniques are used to analyse the complicated systems that arise, including high-field high-frequency electron paramagnetic resonance, inelastic neutron scattering, SQUID magnetometry, and ab initio calculations. The nuclearity of the complexes ranges from dimetallic, to trimetallic, to octametallic. A family of five water- and carboxylate-bridged nickel(II) dimetallics are the focus of a magneto-structural correlation study that succeeds in measuring the magnitude of the exchange interaction despite dominating effects from large zero-field splitting effects. Similar work is reported for four cobalt(II) analogues of these compounds, with the relationship between exchange interactions and geometry also being probed by pressure INS. Charge density studies that combine high resolution X-ray and neutron diffraction studies are reported on cobalt and nickel analogues from the same family of dimetallics, revealing strong evidence for non-direct exchange. A family of four trimetallic triangle complexes containing two nickel(II) ions and one chromium(III) ion bridged by a central fluoride and a total of six carboxylates are reported, and the exchange interactions are elucidated from a global model that accounts for the low-field magnetic, heat capacity, and EPR data. Two new octametallic vanadium(III) wheels—where each pair of adjacent metals are bridged by a fluoride and two carboxylates—are reported along with preliminary results from magnetic measurements and solid state proton NMR spectra, which reveal significant field-dependent effects arising from level crossings at high fields.

abstract: Losses in commercial microwave dielectrics arise from spin excitations in paramagnetic transition metal dopants, at least at reduced temperatures. The magnitude of the loss tangent can be altered by orders of magnitude through the application of an external magnetic field. The goal of this thesis is to produce “smart” dielectrics that can be switched “on” or “off” at small magnetic fields while investigating the influence of transition metal dopants on the dielectric, magnetic, and structural properties. A proof of principle demonstration of a resonator that can switch from a high-Q “on state” to a low-Q “off state” at reduced temperatures is demonstrated in (Al1-xFex)2O3 and La(Al1-xFex)O3. The Fe3+ ions are in a high spin state (S=5/2) and undergo electron paramagnetic resonance absorption transitions that increase the microwave loss of the system. Transitions occur between mJ states with a corresponding change in the angular momentum, J, by ±ħ (i.e., ΔmJ=±1) at small magnetic fields. The paramagnetic ions also have an influence on the dielectric and magnetic properties, which I explore in these systems along with another low loss complex perovskite material, Ca[(Al1-xFex)1/2Nb1/2]O3. I describe what constitutes an optimal microwave loss switchable material induced from EPR transitions and the mechanisms associated with the key properties. As a first step to modeling the properties of high-performance microwave host lattices and ultimately their performance at microwave frequencies, a first-principles approach is used to determine the structural phase stability of various complex perovskites with a range of tolerance factors at 0 K and finite temperatures. By understanding the correct structural phases of these complex perovskites, the temperature coefficient of resonant frequency can be better predicted. A strong understanding of these parameters is expected to open the possibility to produce new types of high-performance switchable filters, time domain MIMO’s, multiplexers, and demultiplexers. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2020

Numerické simulace se staly nedílnou součástí procesu navrhování v nanofotonice, což nevyhnutelně vedlo k vývoji softwaru specializovaného pro tento úkol. Ačkoli je zde celá řada komerčně dostupných produktů, mnohé aplikace vyžadují datovou analýzu, která překračuje standardní výbavu těchto nástrojů. Zpracování výsledků simulací je těžištěm této práce, kdy důraz je kladen zejména na vývoj semianalytických modelů ušitých na míru jednotlivým experimentům. Spolu s lepší shodou mezi teorií a měřeními tyto modely poskytují také cenný vhled do studovaných fyzikálních procesů. Hlavní část této práce je věnována plazmonicky zesílené elektronové paramagnetické rezonanci (PE EPR), nové metodě využívající kovové antény pro zesílení interakce mezi zářením a materiály s magnetickými přechody mezi spinovými stavy. Jsou zde objasněny základní principy řídící tento jev a představen model umožňující rychlou optimalizaci polí antén pro PE EPR spektroskopii tenkých vrstev. Zvláštní pozornost je pak věnována roli indukovaného proudu a možnostem, které nabízí při projekcích do dalekého pole nebo počítání elektromagnetické interakce mezi objekty. Toto je dále demonstrováno na několika aplikacích, jmenovitě fázovém zobrazování metapovrchů pomocí koherencí řízeného holografického mikroskopu, designu optického prvku pro generování pole svazků na bázi metapovrchu a multipólové analýze elektromagnetických vln emitovaných objekty nacházejícími se uvnitř multivrstvy.

In this work two overall subjects were addressed. 1. In recent years high pressure perturbance has become a tool to investigate the folding energy landscape, the volumetric properties and the conformational equilibria of proteins. Conformational states which are not populated at ambient conditions thus become accessible to spectroscopic characterization. In this work a high pressure application was combined with EPR spectroscopy to investigate three spin labeled proteins, BSA from Bos taurus, HisJ from Salmonella enterica serovar Typhimurium and α-synuclein from Homo sapiens. The goal of these studies was to comprehend the influence of pressure on the respective EPR spectra and to identify changes in conformational equilibria and volumetric properties of the investigated proteins. Studies on BSA revealed a negative activation volume for rotational diffusion of the spin labeled site. Moreover, a rotameric equilibrium was derived from the pressure-dependent side chain dynamics and a correlating negative partial molar volume was observed, indicating a shift of the rotameric equilibrium to lesser order. In this regard it was also shown that a chaotropic medium (guanidine hydrochloride) supports the pressure-dependent effect. Spin labeled sites in the substrate binding protein HisJ revealed to be highly influenceable by low pressures between ambient conditions and 200 bar. Pressurization induced oligomerization and precipitation of the protein. Substrate binding revealed differences in pressure-dependence with regard to a decreased precipitation effect but not in relation to oligomerization. The natively unfolded protein α-synuclein plays a key role in Parkinson´s disease and is known for forming β-sheet rich aggregates, so called amyloid fibrils. The experimental data of this work revealed that hydrostatic pressure can induce a non-amyloid aggregation of monomeric α-synuclein which produces an unspecific oligomer. Furthermore, it was shown that α-synuclein amyloid fibrils can be dissolved by hydrostatic pressure. From the pressure dependent conformational equilibrium between the monomer and the fibril form the change of the partial molar volume of the investigated site was determined. 2. The second subject of this work was focused on different import systems, ATP-binding cassette (ABC) transporters and Energy-Coupling-Factor (ECF) transporters, for amino acids, vitamins and metal ions in prokaryotes. Studies on one bacterial ABC and two ECF transporter systems from two different organisms, the histidine ABC-type transporter HisQMP2 from Salmonella enterica serovar Typhimurium, the biotin ECF-type importer BioMNY from Rhodobacter capsulatus and the cobalt-specific ECF-type transporter CbiMNQO from Rhodobacter capsulatus, were performed using DEER and cw EPR spectroscopy. The goal of the studies on HisQMP2 and BioMNY was to shed light on conformations and dynamics connected to their transporter function. Studies on CbiMNQO aimed at the detection of the substrate in the transporter´s substrate binding unit. For HisQMP2 transport cycle dependent conformational changes and interactions with the substrate binding protein HisJ were revealed. Three different distance values between sites H101R1 and H101’R1 in the transporter´s nucleotide binding domains were assigned to the apo-, the ATP-bound and the posthydrolysis state. It was shown that the closed conformation of the nucleotide binding domains is achieved only in the presence of the ligand-bound HisJ which indicates a transmembrane communication of the association of HisJ to the transporter. Furthermore, interspin distances were determined between sites D86R1-A96R1, C197R1-C104R1 and A118R1-G123R1 in the transmembrane domains HisQ and HisM revealing distinguishable conformational states which correlate to the different states of the nucleotide binding sites during the hydrolysis cycle. Measured interspin distances between HisJ and HisM in the HisQMP2 complex showed that interaction only occurred in the closed state of the HisP2 dimer, the nucleotide bound state. Two different, substrate-dependent interactions between site G24R1 in HisJ and site A96R1 in HisQMP2 were observed, revealing that the substrate-free and substrate-bound form of HisJ both associate with HisQMP2. Distance measurements between sites G24R1 and T151R1 in HisJ in the presence and absence of its substrate revealed interspin distance changes that correlate with the proteins open and closed conformation. Investigations on the ECF transporter BioMNY, reconstituted into nanodiscs, revealed a closure and reopening of the nucleotide binding domains between sites H87R1 and H87’R1 using DEER spectroscopy which delivered interspin distance values that correlate with the apo-, the ATP-bound and the posthydrolysis state of the transporter. Further experiments were aimed to shed light on the transporters substrate-translocation mechanism with regard to the so called toppling over mechanism. Unfortunately, the experiments of this work were not able to give a distinct answer with respect to the proposed model because of the transmembrane domains tendency to oligomerize when reconstituted into nanodiscs. In this work we showed that substrate uptake by the substrate binding unit CbiM of the cobalt-specific ECF transporter CbiMNQO depends on the presence of the small transmembrane protein CbiN. Measurements of spin labeled CbiMN in detergent showed oligomerization of CbiM.

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Molecular magnets with different dimensionality, whether they are zero-dimensional singlemolecule magnets (SMM) or one-dimensional single-chain magnets (SCM) are very interesting, since they allow probing the fundamental aspects bordering quantum and classical physics at the nanoscale level. This dissertation covers experimental studies of two Mn-based exchangecoupled molecule-based magnets and two Co-based single-chain magnets, using both dc Halleffect magnetometry and electron paramagnet resonance (EPR) techniques. In these multidimensional systems, the spin of the molecule exhibits quantum mechanical behavior at low temperature. It is quite interesting to observe the effect of magnetic exchange interactions on the magnetic properties of various complexes; hence they strongly affect the magnetic behavior. In this dissertation, the research is initiated with the study of low-magnetic-nuclearity molecules, starting with a spectroscopic study of a significantly anisotropic Mn(IV) monomer. At low temperature the molecule possesses easy-plane type anisotropy of a remarkable magnitude. Although the molecule is not a single-molecule magnet, the remarkable anisotropy can initiate synthesis of newer and better molecular magnets with Mn(IV) as the main building block. Furthermore, the interplay between the magnetic anisotropy and the inter-ion exchange interactions (J) within the molecule are probed for a dimer and a trimer where the magnetic core is comprised of two and three ions respectively. In the Mn-based case of the dimer, the low coupling between the atoms leads to significant state mixing, thus making it impossible to assign the individual spin states to the dimer or to the respective individual Mn(II) ions. In the case of iv the trimer, lowering of the symmetry achieved by fine tuning of the inter-ion exchange interactions leads to relieving of frustration in the antiferromagnetic (AF) triangular Mn(III) system, resulting in a well defined ground state and significant zero field splitting. Also a clear hysteretic behavior observed in this system demonstrates its SMM nature at low temperature. Finally, high-field high-frequency magnetic and spectroscopic studies performed on two cobalt-based SCMs reveal that formation of magnetic domains by exchange interactions within the chain are strongly influenced by thermal fluctuations. The chain possesses a uniaxial anisotropy with the quantization axis lying along the length of the chain. Moreover it is shown that modulation of the magnitude of inter- and intra-chain interactions results in a threedimensional dynamics in one of the samples. Interestingly, detailed dc magnetic studies show a tunable crossover between one- and three-dimensional magnetic dynamics as a function of temperature and/or magnetic field sweep rate. Our voyage through several molecular systems of different dimensionality have allowed us to expand our understanding of the role of exchange interactions on the magnetic behavior in molecular magnetism

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