The electronic spin state (S) of metal ions is fundamental to the performance of magnets, protein cofactors, and magnetic resonance imaging (MRI) contrast agents. The ability to manipulate the spin state of transition metals allows for the development of advanced materials with emergent properties. This following chapters will introduce two...
My research interests, which span organic, inorganic, physical and biochemistry, have focused broadly on photo-, magneto- and redox-active molecules, especially those with potential applications in organic photovoltaics, spintronics and electronics. My research under the joint supervision of Professor Wasielewski and Professor Fraser Stoddart has concentrated upon understanding electronic and magnetic...
The expanding use of nanomaterials in consumer products challenges scientists to understand the impact of these materials before their inevitable release into the environment. In the same way that the widespread use of DDT and asbestos has caused unforeseen negative impacts on both the environment and on human health, the...
Heterogeneous catalysts play a prominent role in our society, used in applications that range from the production of plastics to the catalytic cracking of crude oil. Industrial catalysts are typically made of mixed metal oxides or nanosized metal particles deposited on high surface area supports. Industrially relevant catalytic materials are...
Bulk heterojunction (BHJ) organic photovoltaic (OPV) devices have been extensively studied to achieve power conversion efficiencies well above 10%. New research into alternative materials that allow for cheaper and more industrially viable fabrication of flexible solar cells has been at the forefront of the energy field for the past few...
Three-dimensional (3D) and two-dimensional (2D) hybrid halide perovskites have emerged as front-runners in solar energy conversion applications with the potential to provide low-cost renewable energy. Being at the interface of chemistry, physics, materials science, and electrical engineering, the field of perovskite solar cells has become a top area of interest...
Chemical probes are versatile and unique tools for biomedical research. A chemical probe is simply a selective small-molecule modulator of protein function that allows the user to ask mechanistic and phenotypic questions about its molecular target in biochemical, cell-based or animal studies. Experiments involving selective inhibitors can help delineate key...
Starting materials for natural products, ideally synthesized using low-cost, highly active and selective catalysts, are of great interest to the pharmaceutical industry. Relevant reactions include the synthesis of 1,2-dihydropyridines, reduction of ketones/aldehydes, cleavage of esters, and reduction of amides to amines. Hydroelementation is an important catalytic process that involves H-E...
Photovoltaic technology can help meet the exploding world energy demand in a sustainable and environmentally friendly way. Organic photovoltaics (OPVs) are especially attractive because they can be constructed with low-cost organic content and are amenable to high-throughput large-scale fabrication techniques. Synthetic modification of organic semiconductors has paved way for the...
The discovery and tailoring of new useful organic molecules for applications such as medicine and materials science is highly driven by meaningful developments in chemical methodology, and some of the most impactful advances have invoked catalysis to increase efficiency and specificity. N-heterocyclic carbenes (NHCs) have continuously occupied a prominent space...
The diverse reactivity patterns, unique structural features imparted by the cumulated double bonds, and possibility of axial chirality have garnered allenes considerable attention in organic synthesis. Numerous methods have been described in the literature to afford optically active allenes starting from chiral starting materials, yet catalytic and asymmetric methods to...
High-pressure and -temperature synthesis is a powerful tool for synthesizing new intermetallic compounds that cannot be formed using traditional solid-state syntheses. Such metastable compounds can exhibit unrivaled structural complexity, unique bonding, and unusual properties. In the simplest case, there are many binary systems in which no intermetallic compounds are known....
Noncentrosymmetry (NCS) is a requirement for many properties such as piezoelectricity, pyroelectricity, and nonlinear optical activity like second harmonic generation which are desirable for a variety of commercial applications. One method which has been employed to successfully synthesize NCS compounds utilizes acentric anionic groups, such as oxyfluoride metal complexes, as...
The projected increase in the use of nanomaterials raises concerns about adverse impacts new technologies utilizing these materials may have on the environment. These concerns can be addressed from a chemical perspective by studying how emerging nanomaterials interact with biological systems. Fundamentally, the key interactions for nanomaterial uptake into a...
The tools of computational chemistry allow researchers to gain insight into chemical systems that would be difficult or impossible to gain experimentally. This dissertation discusses the application of several of these computational tools to chemical systems of interest. First, we present several studies of plasmon resonance in Ag nanoclusters using...
Organic Photovoltaic (OPV) materials are of great interest as a low-cost material the purposes of achieving wide spread, solar energy adoption. However, a limiting factor in materials development is the ability to proactively determine the active layer thin film morphology that largely informs device performance. Thus, understanding how materials design...
Organic Photovoltaic (OPV) materials are of great interest as a low-cost material the purposes of achieving wide spread, solar energy adoption. However, a limiting factor in materials development is the ability to proactively determine the active layer thin film morphology that largely informs device performance. Thus, understanding how materials design...
Fused polycyclic scaffolds with three-dimensional complexity from an array of stereocenters compose the core structures of countless natural product families with a variety of desirable biological activity. The development of synthetic methods and strategies to afford rapid access to these structures is essential to expose a wealth of untapped biological...
Self-assembled monolayers as tunable chemical platforms broadly enable the study of the interaction between biological species and synthetic surfaces. Unlike small molecule chemistry where the freely diffusible product can interact with biological targets as an inhibitor or probe, interfacial chemistry allows for the controlled and multi-valent presentation of ligands to...
Spherical nucleic acids (SNAs) are a class of structures composed of spherical nanoparticle cores that are densely functionalized with radially oriented, linear DNA. SNAs exhibit properties that are distinct from those of their linear counterparts. These constructs can readily enter cells, evade nuclease degradation, and bind complementary DNA targets with...