Homo- and Heteronuclear Transition Metal Complexes Supported by Multinucleating Ligands

This dissertation is mainly divided into two sub-parts: organometallic and bioinorganic/materials projects. The approach for the projects involves the use of two different multinucleating ligands to synthesize mono- and multinuclear complexes. Chapter 2 describes the synthesis of a multinucleating tris(phosphinoaryl)benzene ligand used to support mono-nickel and palladium complexes. The isolated mononuclear complexes were observed to undergo intramolecular arene C¬–H to C–P functionalization. The transformation was studied by nuclear magnetic resonance spectroscopy and X-ray crystallography, and represents a rare type of C–H functionalization mechanism, facilitated by the interactions of the group 10 metal with the arene π–system.

Chapter 3 describes the construction of multinickel complexes supported by the same triphosphine ligand from Chapter 2. This chapter shows how the central arene in the ligand’s triarylbenzene framework can interact with dinickel and trinickel moieties in various binding modes. X-ray diffraction studies indicated that all compounds display strong metal–arene interactions. A cofacial triangulo nickel(0) complex supported by this ligand scaffold was also isolated and characterized. This chapter demonstrates the use of an arene as versatile ligand design element for small molecular clusters.

Chapter 4 presents the syntheses of a series of discrete mixed transition metal Mn oxido clusters and their characterization. The synthesis of these oxide clusters displaying two types of transition metals were targeted for systematic metal composition-property studies relevant to mixed transition metal oxides employed in electrocatalysis. A series of heterometallic trimanganese tetraoxido cubanes capped with a redox-active metal [MMn₃O₄] (M = Fe, Co, Ni, Cu) was synthesized starting from a [CaMn₃O₄] precursor and structurally characterized by X-ray crystallography and anomalous diffraction to conclusively determine that M is incorporated at a single position in the cluster. The electrochemical properties of these complexes were studied via cyclic voltammetry. The redox chemistry of the series of complexes was investigated by the addition of a reductant and oxidant. X-ray absorption and electron paramagnetic resonance spectroscopies were also employed to evaluate the product of the oxidation/reduction reaction to determine the site of electron transfer given the presence of two types of redox-active metals. Additional studies on oxygen atom transfer reactivities of [MMn₃O₄] and [MMn₃O₂] series were performed to investigate the effect of the heterometal M in the reaction rates.

Chapter 5 focuses on the use of [CoMn₃O₄] and [NiMn₃O₄] cubane complexes discussed in Chapter 4 as precursors to heterogeneous oxygen evolution reaction (OER) electrocatalysts. These well-defined complexes were dropcasted on electrodes with/without heat treatment, and the OER activities of the resulting films were evaluated. Multiple spectroscopic techniques were performed on the surface of the electrocatalysts to gain insight into the structure-function relationships based on the heterometallic composition. Depending on film preparation, the Co-Mn-oxide was found to change metal composition during catalysis, while the Ni-Mn oxide maintained the NiMn3 ratio. These studies represent the use of discrete heterometallic-oxide clusters as precursors for heterogeneous water oxidation catalysts.

Appendix A describes the ongoing effort to synthesize a series of heteromultimetallic [MMn₃X] clusters (X = O, S, F). Complexes such as [ZnMn₃O], [CoMn₃O], [Mn₃S], and [Mn₄F] have been synthesized and structurally characterized. An amino-bis-oxime ligand (PRABO) has been installed on the [ZnMn₃O] cluster. Upon the addition of O₂, the desymmetrized [ZnMn₃O] cluster only underwent an outer-sphere, one-electron oxidation. Efforts to build and manipulate other heterometallic [MMn₃X] clusters are still ongoing, targeting O₂ binding and reduction. Appendix B summarizes the multiple synthetic approaches to build a [Co₄O₄]-cubane complex relevant to heterogeneous OER electrocatalysis. Starting with the tricobalt cluster [LCo₃(O₂CR)₃] and treatment various strong oxidants that can serve as oxygen atom source in the presence Co²⁺ salt only yielded tricobalt mono–oxo complexes. Appendix C presents the efforts to model the H-cluster framework of [FeFe]-hydrogenase by incorporating a synthetic diiron complex onto a protein-supported or a synthetic ligand-supported [Fe₄S₄]-cluster. The mutant ferredoxin with a [Fe₄S₄]-cluster and triscarbene ligand have been characterized by multiple spectroscopic techniques. The reconstruction of an H-cluster mimic has not yet been achieved, due to the difficulty of obtaining crystallographic evidence and the ambiguity of the EPR results.

Essays in Behavioral Decision Theory

This thesis studies decision making under uncertainty and how economic agents respond to information. The classic model of subjective expected utility and Bayesian updating is often at odds with empirical and experimental results; people exhibit systematic biases in information processing and often exhibit aversion to ambiguity. The aim of this work is to develop simple models that capture observed biases and study their economic implications.

In the first chapter I present an axiomatic model of cognitive dissonance, in which an agent's response to information explicitly depends upon past actions. I introduce novel behavioral axioms and derive a representation in which beliefs are directionally updated. The agent twists the information and overweights states in which his past actions provide a higher payoff. I then characterize two special cases of the representation. In the first case, the agent distorts the likelihood ratio of two states by a function of the utility values of the previous action in those states. In the second case, the agent's posterior beliefs are a convex combination of the Bayesian belief and the one which maximizes the conditional value of the previous action. Within the second case a unique parameter captures the agent's sensitivity to dissonance, and I characterize a way to compare sensitivity to dissonance between individuals. Lastly, I develop several simple applications and show that cognitive dissonance contributes to the equity premium and price volatility, asymmetric reaction to news, and belief polarization.

The second chapter characterizes a decision maker with sticky beliefs. That is, a decision maker who does not update enough in response to information, where enough means as a Bayesian decision maker would. This chapter provides axiomatic foundations for sticky beliefs by weakening the standard axioms of dynamic consistency and consequentialism. I derive a representation in which updated beliefs are a convex combination of the prior and the Bayesian posterior. A unique parameter captures the weight on the prior and is interpreted as the agent's measure of belief stickiness or conservatism bias. This parameter is endogenously identified from preferences and is easily elicited from experimental data.

The third chapter deals with updating in the face of ambiguity, using the framework of Gilboa and Schmeidler. There is no consensus on the correct way way to update a set of priors. Current methods either do not allow a decision maker to make an inference about her priors or require an extreme level of inference. In this chapter I propose and axiomatize a general model of updating a set of priors. A decision maker who updates her beliefs in accordance with the model can be thought of as one that chooses a threshold that is used to determine whether a prior is plausible, given some observation. She retains the plausible priors and applies Bayes' rule. This model includes generalized Bayesian updating and maximum likelihood updating as special cases.

Real-World Social Cognition: Context Effects in Face and Threat Processing

As borne out by everyday social experience, social cognition is highly dependent on context, modulated by a host of factors that arise from the social environment in which we live. While streamlined laboratory research provides excellent experimental control, it can be limited to telling us about the capabilities of the brain under artificial conditions, rather than elucidating the processes that come into play in the real world. Consideration of the impact of ecologically valid contextual cues on social cognition will improve the generalizability of social neuroscience findings also to pathology, e.g., to psychiatric illnesses. To help bridge between laboratory research and social cognition as we experience it in the real world, this thesis investigates three themes: (1) increasing the naturalness of stimuli with richer contextual cues, (2) the potentially special contextual case of social cognition when two people interact directly, and (3) a third theme of experimental believability, which runs in parallel to the first two themes. Focusing on the first two themes, in work with two patient populations, we explore neural contributions to two topics in social cognition. First, we document a basic approach bias in rare patients with bilateral lesions of the amygdala. This finding is then related to the contextual factor of ambiguity, and further investigated together with other contextual cues in a sample of healthy individuals tested over the internet, finally yielding a hierarchical decision tree for social threat evaluation. Second, we demonstrate that neural processing of eye gaze in brain structures related to face, gaze, and social processing is differently modulated by the direct presence of another live person. This question is investigated using fMRI in people with autism and controls. Across a range of topics, we demonstrate that two themes of ecological validity — integration of naturalistic contextual cues, and social interaction — influence social cognition, that particular brain structures mediate this processing, and that it will be crucial to study interaction in order to understand disorders of social interaction such as autism.

Spin wave resonance in ferromagnetic films

The objective of this investigation has been a theoretical and experimental understanding of ferromagnetic resonance phenomena in ferromagnetic thin films, and a consequent understanding of several important physical properties of these films. Significant results have been obtained by ferromagnetic resonance, hysteresis, torque magnetometer, He ion backscattering, and X-ray fluorescence measurements for nickel-iron alloy films.

Taking into account all relevant magnetic fields, including the applied, demagnetizing, effective anisotropy and exchange fields, the spin wave resonance condition applicable to the thin film geometry is presented. On the basis of the simple exchange interaction model it is concluded that the normal resonance modes of an ideal film are expected to be unpinned. The possibility of nonideality near the surface of a real film was considered by means of surface anisotropy field, inhomogeneity in demagnetizing field and inhomogeneity of magnetization models. Numerical results obtained for reasonable parameters in all cases show that they negligibly perturb the resonance fields and the higher order mode shapes from those of the unpinned modes of ideal films for thicknesses greater than 1000 Å. On the other hand for films thinner than 1000 Å the resonance field deviations can be significant even though the modes are very nearly unpinned. A previously unnoticed but important feature of all three models is that the interpretation of the first resonance mode as the uniform mode of an ideal film allows an accurate measurement of the average effective demagnetizing field over the film volume. Furthermore, it is demonstrated that it is possible to choose parameters which give indistinguishable predictions for all three models, making it difficult to uniquely ascertain the source of spin pinning in real films from resonance measurements alone.

Spin wave resonance measurements of 81% Ni-19% Fe coevaporated films 30 to 9000 Å thick, at frequencies from 1 to 8 GHz, at room temperature, and with the static magnetic field parallel and perpendicular to the film plane have been performed. A self-consistent analysis of the results for films thicker than 1000 Å, in which multiple excitations can be observed, shows for the first time that a unique value of exchange constant A can only be obtained by the use of unpinned mode assignments. This evidence and the resonance behavior of films thinner than 1000 Å strongly imply that the magnetization at the surfaces of permalloy films is very weakly pinned. However, resonance measurements alone cannot determine whether this pinning is due to a surface anisotropy, an inhomogeneous demagnetizing field or an inhomogeneous magnetization. The above analysis yields a value of 4πM=10,100 Oe and A = (1.03 ± .05) x 10^-6 erg/cm for this alloy. The ability to obtain a unique value of A suggests that spin wave resonance can be used to accurately characterize the exchange interaction in a ferromagnet.

In an effort to resolve the ambiguity of the source of pinning of the magnetization, a correlation of the ratio of magnetic moment and X-ray film thickness with the value of effective demagnetizing field 4πNM as determined from resonance, for films 45 to 300 Å has been performed. The remarkable agreement of both quantities and a comparison with the predictions of five distinct models, strongly imply that the thickness dependence of both quantities is related to a thickness dependent average saturation magnetization, which is far below 10,100 Oe for very thin films. However, a series of complementary experiments shows that this large decrease of average saturation magnetization cannot be simply explained by either oxidation or interdiffusion processes. It can only be satisfactorily explained by an intrinsic decrease of the average saturation magnetization for very thin films, an effect which cannot be justified by any simple physical considerations.

Recognizing that this decrease of average saturation magnetization could be due to an oxidation process, a correlation of resonance measurements, He ion backscattering, X-ray fluorescence and torque magnetometer measurements, for films 40 to 3500 Å thick has been performed. On basis of these measurements it is unambiguously established that the oxide layer on the surface of purposefully oxidized 81% Ni-19% Fe evaporated films is predominantly Fe-oxide, and that in the oxidation process Fe atoms are removed from the bulk of the film to depths of thousands of angstroms. Extrapolation of results for pure Fe films indicates that the oxide is most likely α-Fe₂O₃. These conclusions are in agreement with results from old metallurgical studies of high temperature oxidation of bulk Fe and Ni-Fe alloys. However, X-ray fluorescence results for films oxidized at room temperature, show that although the preferential oxidation of Fe also takes place in these films, the extent of this process is by far too small to explain the large variation of their average saturation magnetization with film thickness.