Structure-property investigations in urea tethered iodinated triphenylamines.

Herein, we report structural, computational, and conductivity studies on urea-directed self-assembled iodinated triphenylamine (TPA) derivatives. Despite numerous reports of conductive TPAs, the challenges of correlating their solid-state assembly with charge transport properties hinder the efficient design of new materials. In this work, we compare the assembled structures of a methylene urea bridged dimer of di-iodo TPA (1) and the corresponding methylene urea di-iodo TPA monomer (2) with a di-iodo mono aldehyde (3) control. These modifications lead to needle shaped crystals for 1 and 2 that are organized by urea hydrogen bonding, π⋯π stacking, I⋯I, and I⋯π interactions as determined by SC-XRD, Hirshfeld surface analysis, and X-ray photoelectron spectroscopy (XPS). The long needle shaped crystals were robust enough to measure the conductivity by two contact probe methods with 2 exhibiting higher conductivity values (∼6 × 10-7 S cm-1) compared to 1 (1.6 × 10-8 S cm-1). Upon UV-irradiation, 1 formed low quantities of persistent radicals with the simple methylurea 2 displaying less radical formation. The electronic properties of 1 were further investigated using valence band XPS, which revealed a significant shift in the valence band upon UV irradiation (0.5-1.9 eV), indicating the potential of these materials as dopant free p-type hole transporters. The electronic structure calculations suggest that the close packing of TPA promotes their electronic coupling and allows effective charge carrier transport. Our results show that ionic additives significantly improve the conductivity up to ∼2.0 × 10-6 S cm-1 in thin films, enabling their implementation in functional devices such as perovskite or solid-state dye sensitized solar cells.

Stimuli-Modulated Metal Oxidation States in Photochromic MOFs.

Tuning metal oxidation states in metal-organic framework (MOF) nodes by switching between two discrete linker photoisomers via an external stimulus was probed for the first time. On the examples of three novel photochromic copper-based frameworks, we demonstrated the capability of switching between +2 and +1 oxidation states, on demand. In addition to crystallographic methods used for material characterization, the role of the photochromic moieties for tuning the oxidation state was probed via conductivity measurements, cyclic voltammetry, and electron paramagnetic resonance, X-ray photoelectron, and diffuse reflectance spectroscopies. We confirmed the reversible photoswitching activity including photoisomerization rate determination of spiropyran- and diarylethene-containing linkers in extended frameworks, resulting in changes in metal oxidation states as a function of alternating excitation wavelengths. To elucidate the switching process between two states, the photoisomerization quantum yield of photochromic MOFs was determined for the first time. Overall, the introduced noninvasive concept of metal oxidation state modulation on the examples of stimuli-responsive MOFs foreshadows a new pathway for alternation of material properties toward targeted applications.

A Metal-Organic Framework (MOF)-Based Multifunctional Cargo Vehicle for Reactive-Gas Delivery and Catalysis.

The efficient delivery of reactive and toxic gaseous reagents to organic reactions was studied using metal-organic frameworks (MOFs). The simultaneous cargo vehicle and catalytic capabilities of several MOFs were probed for the first time using the examples of aromatization, aminocarbonylation, and carbonylative Suzuki-Miyaura coupling reactions. These reactions highlight that MOFs can serve a dual role as a gas cargo vehicle and a catalyst, leading to product formation with yields similar to reactions employing pure gases. Furthermore, the MOFs can be recycled without sacrificing product yield, while simultaneously maintaining crystallinity. The reported findings were supported crystallographically and spectroscopically (e.g., diffuse reflectance infrared Fourier transform spectroscopy), foreshadowing a pathway for the development of multifunctional MOF-based reagent-catalyst cargo vessels for reactive gas reagents as an attractive alternative to the use of toxic pure gases or gas generators.

Mixed-metal hybrid ultramicroporous material (HUM) precursor to graphene-supported tetrataenite as a highly active and durable NPG catalyst for the OER.

Current interest in investigating non-precious group (NPG) metals for catalyzing the oxygen evolution reaction (OER) has revealed that doping of Ni hydroxides with Fe results in the dramatic enhancement of catalytic activity. Herein, a facile pathway to construct tetrataenite, an NiFe alloy of extraterrestrial origin and to address the limited electrical conductivity of metal oxides/hydroxides by directly constructing them atop graphene sheets is described. In this approach, a one-pot, bottom-up assembly of hybrid ultramicroporous materials (HUMs) was carried out, in the presence of suspended graphene (G), to homogeneously deposit the HUMs on unmodified graphene sheets, affording HUMs@G. Single metal (SIFSIX-3-Ni@G) and mixed metal (SIFSIX-3-NiFe@G) HUMs can be readily synthesized from their respective metal salts to afford a well-designed catalyst for the OER. The pyrolysis of SIFSIX-3-NiFe@G resulted in the deposition of the nanoalloy tetrataenite on G, demonstrating an exceptionally low OER onset potential of 1.44 V vs. RHE and reduced overpotential at 10 mA cm-2 (η10 = 266 mV). The synergy between the composition of the active catalyst and the electronically conductive support was attained by designing a reaction system encoding the self-assembly of a crystalline pre-catalyst on G sheets.

Promoting Atomically Dispersed MnN4 Sites via Sulfur Doping for Oxygen Reduction: Unveiling Intrinsic Activity and Degradation in Fuel Cells.

Carbon supported and nitrogen coordinated single Mn site (Mn-N-C) catalysts are the most desirable platinum group metal (PGM)-free cathode catalysts for proton-exchange membrane fuel cells (PEMFCs) due to their insignificant Fenton reactions (vs. Fe), earth abundances (vs. Co), and encouraging activity and stability. However, current Mn-N-C catalysts suffer from high overpotential due to low intrinsic activity and less dense MnN4 sites. Herein, we present a sulfur-doped Mn-N-C catalyst (Mn-N-C-S) synthesized through an effective adsorption-pyrolysis process. Using electron microscopy and X-ray absorption spectroscopy (XAS) techniques, we verify the uniform dispersion of MnN4 sites and confirm the effect of S doping on the Mn-N coordination. The Mn-N-C-S catalyst exhibits a favorable oxygen reduction reaction (ORR) activity in acidic media relative to the S-free Mn-N-C catalyst. The corresponding membrane electrode assembly (MEA) generates enhanced performance with a peak power density of 500 mW cm-2 under a realistic H2/air environment. The constant voltage tests of fuel cells confirm the much-enhanced stability of the Mn-N-C-S catalyst compared to the Fe-N-C and Fe-N-C-S catalysts. The electron microscopy and Fourier transform XAS analyses provide insights into catalyst degradation associated with Mn oxidation and agglomeration. The theoretical calculation elucidates that the promoted ORR activity is mainly attributed to the spatial effect stemmed from the repulsive interaction between the ORR intermediates and adjacent S dopants.

Boron-hyperdoped silicon for the selective oxidative dehydrogenation of propane to propylene.

Boron containing catalysts have great potential in the oxidative dehydrogenation of propane. Herein, a series of 15, 25 and 42 at% boron-hyperdoped silicon catalysts synthesized by laser pyrolysis was studied. Boron-hyperdoped silicon samples showed >6 times higher propylene productivity than commercial h-BN at 450 °C.

Heterometallic multinuclear nodes directing MOF electronic behavior.

Metal node engineering in combination with modularity, topological diversity, and porosity of metal-organic frameworks (MOFs) could advance energy and optoelectronic sectors. In this study, we focus on MOFs with multinuclear heterometallic nodes for establishing metal-property trends, i.e., connecting atomic scale changes with macroscopic material properties by utilization of inductively coupled plasma mass spectrometry, conductivity measurements, X-ray photoelectron and diffuse reflectance spectroscopies, and density functional theory calculations. The results of Bader charge analysis and studies employing the Voronoi-Dirichlet partition of crystal structures are also presented. As an example of frameworks with different nodal arrangements, we have chosen MOFs with mononuclear, binuclear, and pentanuclear nodes, primarily consisting of first-row transition metals, that are incorporated in HHTP-, BTC-, and NIP-systems, respectively (HHTP3- = triphenylene-2,3,6,7,10,11-hexaone; BTC3- = 1,3,5-benzenetricarboxylate; and NIP2- = 5-nitroisophthalate). Through probing framework electronic profiles, we demonstrate structure-property relationships, and also highlight the necessity for both comprehensive analysis of trends in metal properties, and novel avenues for preparation of heterometallic multinuclear isoreticular structures, which are critical components for on-demand tailoring of properties in heterometallic systems.

Tuning the Chemical Environment within the UiO-66-NH2 Nanocages for Charge-Dependent Contaminant Uptake and Selectivity.

The remarkable water stability of Zr-carboxylate-based metal-organic frameworks (MOFs) stimulated considerable interest toward their utilization in aqueous phase applications. The origin of such stability is probed here through pH titration and pKa modeling. A unique feature of the Zr6(µ3-OH)4(µ3-O)4(RCO2)12 cluster is the Zr-bridging oxo/hydroxyl groups, demonstrating several pKa values that appear to provide for the water stability at a wide range of pH. Accordingly, the tunability of the cage/surface charge of the MOF can feasibly be controlled through careful adjustment of solution pH. Such high stability, and facile control over cage/surface charge, can additionally be augmented through introducing chemical functionalities lining the cages of the MOF, specifically amine groups in the UiO-66-NH2 presented herein. The variable protonation states of the Zr cluster and the pendant amino groups, their H-bond donor/acceptor characteristics, and their electrostatic interactions with guest molecules were effectively utilized in controlled experiments to demonstrate high uptake of model guest molecules (137 mg/g for Cr(VI), 1275 mg/g for methylene blue, and 909 mg/g for methyl orange). Additionally, a practical form of the silica-supported MOF, UiO-66-NH2@SiO2, constructed in under 2 h reaction time, is described, generating a true platform microporous sorbent for practical use in demanding applications.

Thermodynamics and Electronic Properties of Heterometallic Multinuclear Actinide-Containing Metal-Organic Frameworks with "Structural Memory".

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 to An-MOF thermochemistry, enthalpies of formation were determined for the organic linkers, 2,2'-dimethylbiphenyl-4,4'-dicarboxylic acid (H2Me2BPDC) and biphenyl-4,4'-dicarboxylic acid (H2BPDC), which are commonly used building blocks for MOF preparation. The electronic structure of the first example of An-MOF with mixed-metal AnAn'-nodes was influenced through coordination of transition metals as shown by the density of states near the Fermi edge, changes in the Tauc plot, conductivity measurements, and theoretical calculations. The "structural memory" effect (i.e., solvent-directed crystalline-amorphous-crystalline structural dynamism) was demonstrated as a function of node coordination degree, which is the number of organic linkers per metal node. Remarkable three-month water stability was reported for Th-containing frameworks herein, and the mechanism is also considered for improvement of the behavior of a U-based framework in water. Mechanistic aspects of capping linker installation were highlighted through crystallographic characterization of the intermediate, and theoretical calculations of free energies of formation (ΔGf) for U- and Th-MOFs with 10- and 12-coordinated secondary building units (SBUs) were performed to elucidate experimentally observed transformations during the installation processes. Overall, these results are the first thermochemical, electronic, and mechanistic insights for a relatively young class of actinide-containing frameworks.

Cs3REIIIGe3O9 (RE = Pr, Nd, and Sm-Yb) and Cs8TbIII2TbIVGe9O27: A Rare Example of a Mixed-Valent Tb(III)/Tb(IV) Oxide.

Single crystals of 12 new cesium rare earth germanates crystallizing in two new structure types were grown from a CsCl/CsF flux. Cs3REGe3O9 (RE = Pr, Nd, and Sm-Yb), a new family of germanates that form for almost the entire series of rare earth elements, crystallizes in orthorhombic space group Pna21 with lattice parameters in the following ranges: a = 13.7033(4)-14.022(2) Å, b = 7.0545(2)-7.2405(12) Å, and c = 12.6672(4)-12.836(2) Å. Surprisingly, the Tb reaction yielded both Cs3TbGe3O9 and Cs8Tb3Ge9O27, a rare example of a mixed-valent Tb(III)/Tb(IV) compound. Cs8Tb3Ge9O27 crystallizes in space group P3 with the following lattice parameters: a = 11.2906(4) Å, and c = 7.9605(3) Å. The mixed-valent oxidation state of Tb was confirmed by structure solution, bond-valence sums, X-ray photoelectron spectroscopy data, and magnetic data. Optical and magnetic properties are reported for both sets of compounds.

Connecting Wires: Photoinduced Electronic Structure Modulation in Metal-Organic Frameworks.

Electronic structure modulation of metal-organic frameworks (MOFs) through the connection of linker "wires" as a function of an external stimulus is reported for the first time. The established correlation between MOF electronic properties and photoisomerization kinetics as well as changes in an absorption profile is unprecedented for extended well-defined structures containing coordinatively integrated photoresponsive linkers. The presented studies were carried out on both single crystal and bulk powder with preservation of framework integrity. An LED-containing electric circuit, in which the switching behavior was driven by the changes in MOF electronic profile, was built for visualization of experimental findings. The demonstrated concept could be used as a blueprint for development of stimuli-responsive materials with dynamically controlled electronic behavior.

A Ni-loaded, metal-organic framework-graphene composite as a precursor for in situ electrochemical deposition of a highly active and durable water oxidation nanocatalyst.

A novel approach to construct a highly active and durable Ni(OH)2 nanoparticle/graphene hybrid electrocatalyst for the oxygen-evolution reaction (OER) is reported. This approach utilized the Ni-loaded, graphene-supported, Zr-carboxylate metal-organic framework (UiO-66-NH2-Ni@G) as a sacrificial pre-catalyst to engender the true catalyst in an electrochemical surface restructuring process. This has resulted in an exceptionally active (η10 = 0.38 V vs. RHE) and highly durable OER catalyst, and can potentially be employed as a viable facile alternative to the commonly utilized pyrolysis of MOFs, to access heterogenous catalysts for demanding electrochemically-promoted reactions.

Stack the Bowls: Tailoring the Electronic Structure of Corannulene-Integrated Crystalline Materials.

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 in comparison with the parent framework. In addition to the first report of alkyne-azide cycloaddition utilized for corannulene immobilization in the solid state, we also probed the charge transfer rate within the Marcus theory as a function of mutual πB orientation for the first time, as well as shed light on the density of states near the Fermi edge. These studies could foreshadow new avenues for πB utilization for the development of optoelectronic devices or a route for highly efficient porous electrodes.

Na2(UO2)(BO3): An All-Uranium(V) Borate Synthesized under Mild Hydrothermal Conditions.

The first entirely pentavalent uranium borate, Na2(UO2)(BO3), was synthesized under mild hydrothermal conditions. The single-crystal structure was solved in the orthorhombic space group Cmcm with a = 10.0472(3) Å, b = 6.5942(2) Å, and c = 6.9569(2) Å. Magnetic susceptibility measurements revealed an antiferromagnetic transition at 12 K and an effective magnetic moment of 2.33 µB. Density functional theory calculations indicated dynamic stability of the structure above 0 K.

Preferentially Oriented Ag Nanocrystals with Extremely High Activity and Faradaic Efficiency for CO2 Electrochemical Reduction to CO.

Selective electrochemical reduction of CO2 is one of the most important processes to study because of its promise to convert this greenhouse gas to value-added chemicals at low cost. In this work, a simple anodization treatment was devised that first oxidizes Ag to Ag2CO3, then uses rapid electrochemical reduction to create preferentially oriented nanoparticles (PONs) of metallic Ag (PON-Ag) with high surface area as well as high activity and very high selectivity for the reduction of CO2 to CO. The PON-Ag catalyst was dominated by (110) and (100) orientation, which allowed PON-Ag to achieve a CO Faradaic efficiency of 96.7% at an operating potential of -0.69 V vs RHE. This performance is not only significantly higher than that of polycrystalline Ag (60% at -0.87 V vs RHE) but also represents one of the best combinations of activity and selectivity achieved to date - all with a very simple, scalable approach to electrode fabrication.

Multifaceted Modularity: A Key for Stepwise Building of Hierarchical Complexity in Actinide Metal-Organic Frameworks.

Growing necessity for efficient nuclear waste management is a driving force for development of alternative architectures toward fundamental understanding of mechanisms involved in actinide (An) integration inside extended structures. In this manuscript, metal-organic frameworks (MOFs) were investigated as a model system for engineering radionuclide containing materials through utilization of unprecedented MOF modularity, which cannot be replicated in any other type of materials. Through the implementation of recent synthetic advances in the MOF field, hierarchical complexity of An-materials was built stepwise, which was only feasible due to preparation of the first examples of actinide-based frameworks with "unsaturated" metal nodes. The first successful attempts of solid-state metathesis and metal node extension in An-MOFs are reported, and the results of the former approach revealed drastic differences in chemical behavior of extended structures versus molecular species. Successful utilization of MOF modularity also allowed us to structurally characterize the first example of bimetallic An-An nodes. To the best of our knowledge, through combination of solid-state metathesis, guest incorporation, and capping linker installation, we were able to achieve the highest Th wt % in mono- and biactinide frameworks with minimal structural density. Overall, the combination of a multistep synthetic approach with homogeneous actinide distribution and moderate solvothermal conditions could make MOFs an exceptionally powerful tool to address fundamental questions responsible for chemical behavior of An-based extended structures and, therefore, shed light on possible optimization of nuclear waste administration.

Tailoring the Oxygen Reduction Activity of Hemoglobin through Immobilization within Microporous Organic Polymer-Graphene Composite.

A facile one-pot, bottom-up approach to construct composite materials of graphene and a pyrimidine-based porous-organic polymer (PyPOP), as host for immobilizing human hemoglobin (Hb) biofunctional molecules, is reported. The graphene was selected because of its excellent electrical conductivity, while the PyPOP was utilized because of its pronounced permanent microporosity and chemical functionality. This approach enabled enclathration of the hemoglobin within the microporous composite through a ship-in-a-bottle process, where the composite of the PyPOP@G was constructed from its molecular precursors, under mild reaction conditions. The composite-enclathrated Fe-protoporphyrin-IX demonstrated electrocatalytic activity toward oxygen reduction, as a functional metallocomplex, yet with a distinct microenvironment provided by the globin protein. This approach delineates a pathway for platform microporous functional solids, where fine-tuning of functionality is facilitated by judicious choice of the active host molecules or complexes, targeting specific application.

Hierarchical Corannulene-Based Materials: Energy Transfer and Solid-State Photophysics.

We report the first example of a donor-acceptor corannulene-containing hybrid material with rapid ligand-to-ligand energy transfer (ET). Additionally, we provide the first time-resolved photoluminescence (PL) data for any corannulene-based compounds in the solid state. Comprehensive analysis of PL data in combination with theoretical calculations of donor-acceptor exciton coupling was employed to estimate ET rate and efficiency in the prepared material. The ligand-to-ligand ET rate calculated using two models is comparable with that observed in fullerene-containing materials, which are generally considered for molecular electronics development. Thus, the presented studies not only demonstrate the possibility of merging the intrinsic properties of π-bowls, specifically corannulene derivatives, with the versatility of crystalline hybrid scaffolds, but could also foreshadow the engineering of a novel class of hierarchical corannulene-based hybrid materials for optoelectronic devices.