A5034371938- X-ray Diffraction in Crystallography
- Crystallization and Solubility Studies
- Metal-Organic Frameworks: Synthesis and Applications
- Luminescence and Fluorescent Materials
- Chalcogenide Semiconductor Thin Films
- Covalent Organic Framework Applications
- Fullerene Chemistry and Applications
- Crystallography and molecular interactions
- Synthesis and Properties of Aromatic Compounds
- Molecular Sensors and Ion Detection
- Catalytic Processes in Materials Science
- Radioactive element chemistry and processing
- Advanced Nanomaterials in Catalysis
- Semiconductor Quantum Structures and Devices
- Quantum Dots Synthesis And Properties
- Advanced Thermoelectric Materials and Devices
- Photochromic and Fluorescence Chemistry
- Machine Learning in Materials Science
- Nanoplatforms for cancer theranostics
- Graphene research and applications
- Supramolecular Self-Assembly in Materials
- Nanocluster Synthesis and Applications
- Semiconductor materials and interfaces
- Fluorine in Organic Chemistry
- Advanced Semiconductor Detectors and Materials
Center for Integrated Nanotechnologies
2020-2024
Los Alamos National Laboratory
2019-2024
University of South Carolina
2015-2023
University of South Carolina Sumter
2015-2018
Lomonosov Moscow State University
2011-2018
Moscow State University
2010-2013
Voronezh State University
2001-2012
The development of porous well-defined hybrid materials (e.g., metal–organic frameworks or MOFs) will add a new dimension to wide number applications ranging from supercapacitors and electrodes “smart” membranes thermoelectrics. From this perspective, the understanding tailoring electronic properties MOFs are key fundamental challenges that could unlock full potential these materials. In work, we focused on insights responsible for three distinct classes bimetallic systems, Mx–yM′y-MOFs,...
Stimuli-responsive materials are vital for addressing emerging demands in the advanced technology sector as well current industrial challenges. Here, we report first time that coordinative integration of photoresponsive building blocks possessing photochromic spiropyran and diarylethene moieties within a rigid scaffold metal–organic frameworks (MOFs) could control photophysics, particular, cycloreversion kinetics, with level is not accessible solid state or solution. On series photoactive...
Growing necessity for efficient nuclear waste management is a driving force development of alternative architectures toward fundamental understanding mechanisms involved in actinide (An) integration inside extended structures. In this manuscript, metal–organic frameworks (MOFs) were investigated as model system engineering radionuclide containing materials through utilization unprecedented MOF modularity, which cannot be replicated any other type materials. Through the implementation recent...
This perspective focuses on the synthesis, characterization, and modeling of three classes hierarchical materials with potential for sequestering radionuclides: nanoparticles, porous frameworks, crystalline salt inclusion phases. The scientific impact structures development underlying crystal chemistry is discussed as laying groundwork design, local structure control, synthesis new forms matter tailored properties. requires necessary understanding such complex through integrated studies that...
We have developed an integrated approach that combines synthesis, X-ray photoelectron spectroscopy (XPS) studies, and theoretical calculations for the investigation of active unsaturated metal sites (UMS) in copper-based metal–organic frameworks (MOFs). Specifically, extensive reduction Cu+2 to Cu+1 at MOF nodes was achieved. Introduction mixed valence copper resulted significant changes band structure increased density states near Fermi edge, thereby altering electronic properties...
Electronic structure modulation of metal-organic frameworks (MOFs) through the connection linker "wires" as a function an external stimulus is reported for first time. The established correlation between MOF electronic properties and photoisomerization kinetics well changes in absorption profile unprecedented extended well-defined structures containing coordinatively integrated photoresponsive linkers. presented studies were carried out on both single crystal bulk powder with preservation...
In this review, we highlight how recent advances in the field of actinide structural chemistry metal–organic frameworks (MOFs) could be utilized towards investigations relative to efficient nuclear waste administration, driven by interest development novel actinide-containing architectures as well concerns regarding environmental pollution and storage.
In this Perspective, we highlight how recent studies of heterometallic metal–organic frameworks (MOFs) could lead to advances the energy landscape. The ability merge inherent properties MOFs, including their modularity, porosity, versatility, high surface area, and structural tunability, with engineer metal nodes benefit both classical realm MOF applications as well shift toward electronic structure studies. This Perspective is intended provide a glimpse into advances, challenges, future...
Chromophores with a benzylidene imidazolidinone core define the emission profile of commonly used biomarkers such as green fluorescent protein (GFP) and its analogues. In this communication, artificially engineered porous scaffolds have been shown to mimic β-barrel structure, maintaining fluorescence response conformational rigidity GFP-like chromophores. particular, we demonstrated that maximum in our artificial is similar those observed spectra natural GFP-based systems. To correlate...
Thermodynamic studies of actinide-containing metal-organic frameworks (An-MOFs), reported herein for the first time, are a step toward addressing challenges related to effective nuclear waste administration. In addition An-MOF thermochemistry, enthalpies formation were determined organic linkers, 2,2'-dimethylbiphenyl-4,4'-dicarboxylic acid (H2Me2BPDC) and biphenyl-4,4'-dicarboxylic (H2BPDC), which commonly used building blocks MOF preparation. The electronic structure example with...
Merging the intrinsic properties of fullerene (buckyball) and corannulene (buckybowl) derivatives with inherent crystalline metal- covalent-organic frameworks (MOFs COFs), including their modularity, porosity, versatility, high surface area, structural tunability, opens a pathway to unlock novel class fulleretic materials. Despite great interest in MOFs COFs, as well derivatives, this perspective is first overview focusing solely on fullerene- corannulene-containing frameworks, highlighting...
Abstract Efficient multiple‐chromophore coupling in a crystalline metal–organic scaffold was achieved by mimicking protein system possessing 100 % energy‐transfer (ET) efficiency between green fluorescent variant and cytochrome b 562 . The two approaches developed for ET relied on the construction of coordination assemblies host–guest coupling. Based time‐resolved photoluminescence measurements combination with calculations spectral overlap function Förster radius, we demonstrated that both...
We synthesized PbS/CdS core/shell quantum dots (QDs) to have functional single-emitter properties for room-temperature, solid-state operation in the telecom O and S bands. Two shell-growth methods—cation exchange successive ionic layer adsorption reaction (SILAR)—were employed prepare QD heterostructures with shells of 2–16 monolayers. QDs were sufficiently bright stable resolve photoluminescence (PL) spectra representing both bands from single nanocrystals using standard detection methods,...
A porous crystalline corannulene-containing scaffold, which combines the periodicity, dimensionality, and structural modularity of hybrid frameworks with intrinsic properties redox-active π-bowls, has been prepared. Single-crystal powder X-ray diffraction, ab initio density functional theory computations, gas sorption analysis, fluorescence spectroscopy, cyclic voltammetry were employed to study novel corannulene derivatives buckybowl-based materials. diffraction studies revealed...
Abstract Herein, we report the first example of a crystalline metal–donor–fullerene framework, in which control donor–fullerene mutual orientation was achieved through chemical bond formation, particular, by metal coordination. The 13 C cross‐polarization magic‐angle spinning NMR spectroscopy, X‐ray diffraction, and time‐resolved fluorescence spectroscopy were performed for comprehensive structural analysis energy‐transfer (ET) studies fulleretic donor–acceptor scaffold. Furthermore,...
We report the first examples of purely organic donor-acceptor materials with integrated π-bowls (πBs) that combine not only crystallinity and high surface areas but also exhibit tunable electronic properties, resulting in a four-orders-of-magnitude conductivity enhancement comparison parent framework. In addition to alkyne-azide cycloaddition utilized for corannulene immobilization solid state, we probed charge transfer rate within Marcus theory as function mutual πB orientation time, well...
Engineering of novel systems capable efficient energy capture and transfer in a predesigned pathway could potentially boost applications varying from organic photovoltaics to catalytic platforms have implications for sustainability green chemistry. While light-harvesting properties different materials been studied decades, recently, there has great progress the understanding modeling short- long-range processes through utilization metal-organic frameworks (MOFs). In this Forum Article,...
We report the first example of a donor-acceptor corannulene-containing hybrid material with rapid ligand-to-ligand energy transfer (ET). Additionally, we provide time-resolved photoluminescence (PL) data for any corannulene-based compounds in solid state. Comprehensive analysis PL combination theoretical calculations exciton coupling was employed to estimate ET rate and efficiency prepared material. The calculated using two models is comparable that observed fullerene-containing materials,...
Photophysics tunability through alteration of framework aperture (metal–organic (MOF) = variable; guest constant) was probed for the first time in comparison with previously explored concepts (MOF constant; variable). In particular, analysis confinement effect on a photophysical response integrated 5-(3-chlorobenzylidene)-2,3-dimethyl-3,5-dihydro-4H-imidazol-4-one (Cl-BI) chromophore allowed us to establish photophysics–aperture relationship. To shed light observed correlation, confined...
Organic chromophores that exhibit aggregation-induced emission (AIE) are of interest for applications in displays, lighting, and sensing, because they can maintain efficient at high molecular concentrations the solid state. Such advantages over conventional could allow thinner conversion layers AIE to be realized, with benefits terms efficiency optical outcoupling, thermal management, response times. However, it is difficult create large-area quality thin films efficiently performing...
For the first time, we report ability to control radionuclide species release kinetics in metal-organic frameworks (MOFs) as a function of postsynthetic capping linker installation, which is essential for understanding MOF potential viable wasteform materials or versatile platforms sensing, leaching, and sequestration. The radiation damage prepared under γ has also been studied. We envision that presented studies are steps toward utilization reported scaffolds more efficient nuclear waste...
The first lanthanide dinitrogen photoswitch [(C5Me4H)2(THF)Lu]2(μ–η2:η2-N2), 1, is reported. 1 a unique example of controlled isomerization between side-on and end-on coordination modes [N2]2– in bimetallic lutetium complex that results photochromism. Near-infrared light (NIR) was used to promote this effect, as evidenced by single X-ray diffraction (XRD) connectivity Raman data, generating the bound isomer, [(C5Me4H)2(THF)Lu]2(μ–η1:η1-N2), 2. Although different ligands coordinating solvents...
Photophysics and dynamics of chromophores with a benzylidene imidazolinone core, responsible for emission green fluorescent protein variants, were studied as function host topology by three approaches. Coordinative, non-coordinative, "fastened" immobilization utilized to study chromophore emission. Variable-temperature quadrupolar spin-echo 2H NMR spectra are reported.