40 research outputs found
Oxidation chemistry of d^0 organometallic complexes
Electron-transfer processes can play an important role in organometallic chemistry. Herein, we demonstrate that even d^0 organometallic complexes exhibit a rich redox chemistry and present electrochemical, kinetics, and stereochemical studies that establish a general outer-sphere oxidation process for d^0 group 4 metallocene complexes. This oxidation chemistry closely parallels the reported LMCT photochemistry of these complexes
Ternary Nitride Semiconductors in the Rocksalt Crystal Structure
Inorganic nitrides with wurtzite crystal structures are well-known
semiconductors used in optoelectronic devices. In contrast, rocksalt-based
nitrides are known for their metallic and refractory properties. Breaking this
dichotomy, here we report on ternary nitride semiconductors with rocksalt
crystal structures, remarkable optoelectronic properties, and the general
chemical formula MgTMN (TM=Ti, Zr, Hf, Nb). These compounds form
over a broad metal composition range and our experiments show that Mg-rich
compositions are nondegenerate semiconductors with visible-range optical
absorption onsets (1.8-2.1 eV). Lattice parameters are compatible with growth
on a variety of substrates, and epitaxially grown MgZrN exhibits
remarkable electron mobilities approaching 100 cmVs. Ab
initio calculations reveal that these compounds have disorder-tunable optical
properties, large dielectric constants and low carrier effective masses that
are insensitive to disorder. Overall, these experimental and theoretical
results highlight MgTMN rocksalts as a new class of
semiconductor materials with promising properties for optoelectronic
applications
A Map of the Inorganic Ternary Metal Nitrides
Exploratory synthesis in novel chemical spaces is the essence of solid-state
chemistry. However, uncharted chemical spaces can be difficult to navigate,
especially when materials synthesis is challenging. Nitrides represent one such
space, where stringent synthesis constraints have limited the exploration of
this important class of functional materials. Here, we employ a suite of
computational materials discovery and informatics tools to construct a large
stability map of the inorganic ternary metal nitrides. Our map clusters the
ternary nitrides into chemical families with distinct stability and
metastability, and highlights hundreds of promising new ternary nitride spaces
for experimental investigation--from which we experimentally realized 7 new Zn-
and Mg-based ternary nitrides. By extracting the mixed metallicity, ionicity,
and covalency of solid-state bonding from the DFT-computed electron density, we
reveal the complex interplay between chemistry, composition, and electronic
structure in governing large-scale stability trends in ternary nitride
materials
Oxidation chemistry of d^0 organometallic complexes
Electron-transfer processes can play an important role in organometallic chemistry. Herein, we demonstrate that even d^0 organometallic complexes exhibit a rich redox chemistry and present electrochemical, kinetics, and stereochemical studies that establish a general outer-sphere oxidation process for d^0 group 4 metallocene complexes. This oxidation chemistry closely parallels the reported LMCT photochemistry of these complexes
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Heterogenization of Homogeneous Catalysts: the Effect of the Support
We have studied the influence of placing a soluble, homogeneous catalyst onto a solid support. We determined that such a 'heterogenized' homogeneous catalyst can have improved activity and selectivity for the asymmetric hydrogenation of enamides to amino acid derivatives. The route of heterogenization of RhDuPhos(COD){sup +} cations occurs via electrostatic interactions with anions that are capable of strong hydrogen bonding to silica surfaces. This is a novel approach to supported catalysis. Supported RhDuPhos(COD){sup +} is a recyclable, non-leaching catalyst in non-polar media. This is one of the few heterogenized catalysts that exhibits improved catalytic performance as compared to its homogeneous analog
Characterisation of monoclonal antibodies specific for hamster leukocyte differentiation molecules
Flow cytometry was used to identify mAbs that recognize conserved epitopes on hamster leukocyte differentiation molecules (hLDM) and also to characterize mAbs developed against hLDM. Initial screening of mAbs developed against LDMs in other species yielded mAbs specific for the major histocompatibility (MHC) II molecule, CD4 and CD18. Screening of sets of mAbs developed against hLDM yielded 22 new mAbs, including additional mAbs to MHC II molecules and mAbs that recognize LDMs expressed on all leukocytes, granulocytes, all lymphocytes, all T cells, a subset of T cells, or on all B cells. Based on comparison of the pattern of expression of LDMs expressed on all hamster leukocytes with the patterns of expression of known LDMs in other species, as detected by flow cytometry (FC), four mAbs are predicted to recognize CD11a, CD44, and CD45. Cross comparison of mAbs specific for a subset of hamster T cells with a cross reactive mAb known to recognize CD4 in mice and one recognising CD8 revealed they recognize CD4. The characterization of these mAbs expands opportunities to use hamsters as an additional model species to investigate the mechanisms of immunopathogenesis of infectious diseases
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Novel phase diagram behavior and materials design in heterostructural semiconductor alloys
Structure and composition control the behavior of materials. Isostructural alloying is historically an extremely successful approach for tuning materials properties, but it is often limited by binodal and spinodal decomposition, which correspond to the thermodynamic solubility limit and the stability against composition fluctuations, respectively. We show that heterostructural alloys can exhibit a markedly increased range of metastable alloy compositions between the binodal and spinodal lines, thereby opening up a vast phase space for novel homogeneous single-phase alloys. We distinguish two types of heterostructural alloys, that is, those between commensurate and incommensurate phases. Because of the structural transition around the critical composition, the properties change in a highly nonlinear or even discontinuous fashion, providing a mechanism for materials design that does not exist in conventional isostructural alloys. The novel phase diagram behavior follows from standard alloy models using mixing enthalpies from first-principles calculations. Thin-film deposition demonstrates the viability of the synthesis of these metastable single-phase domains and validates the computationally predicted phase separation mechanism above the upper temperature bound of the nonequilibrium single-phase region
Polymer synthesis and organotransition metal chemistry
Mechanistic and synthetic studies in organometallic chemistry have provided considerable insight into olefin metathesis and Ziegler-Natta polymerization. New homogeneous olefin metathesis catalysts based on high oxidation state transition metals have opened new opportunities in polymer synthesis by providing unprecedented control in ring-opening polymerization of cyclic alkenes. The recent development of living coordinative polymerization systems has led to the preparation of a number of new, interesting materials, including block copolymers, conducting polymers or precursors, and ionophoric polymeric substrates