Compression of curium pyrrolidine-dithiocarbamate enhances covalency.

Curium is unique in the actinide series because its half-filled 5f 7 shell has lower energy than other 5f n configurations, rendering it both redox-inactive and resistant to forming chemical bonds that engage the 5f shell1-3. This is even more pronounced in gadolinium, curium's lanthanide analogue, owing to the contraction of the 4f orbitals with respect to the 5f orbitals4. However, at high pressures metallic curium undergoes a transition from localized to itinerant 5f electrons5. This transition is accompanied by a crystal structure dictated by the magnetic interactions between curium atoms5,6. Therefore, the question arises of whether the frontier metal orbitals in curium(III)-ligand interactions can also be modified by applying pressure, and thus be induced to form metal-ligand bonds with a degree of covalency. Here we report experimental and computational evidence for changes in the relative roles of the 5f/6d orbitals in curium-sulfur bonds in [Cm(pydtc)4]- (pydtc, pyrrolidinedithiocarbamate) at high pressures (up to 11 gigapascals). We compare these results to the spectra of [Nd(pydtc)4]- and of a Cm(III) mellitate that possesses only curium-oxygen bonds. Compared with the changes observed in the [Cm(pydtc)4]- spectra, we observe smaller changes in the f-f transitions in the [Nd(pydtc)4]- absorption spectrum and in the f-f emission spectrum of the Cm(III) mellitate upon pressurization, which are related to the smaller perturbation of the nature of their bonds. These results reveal that the metal orbital contributions to the curium-sulfur bonds are considerably enhanced at high pressures and that the 5f orbital involvement doubles between 0 and 11 gigapascal. Our work implies that covalency in actinides is complex even when dealing with the same ion, but it could guide the selection of ligands to study the effect of pressure on actinide compounds.

Molecular Orientation and Energy Transfer Dynamics of a Metal Oxide Bound Self-Assembled Trilayer.

Self-assembly of molecular multilayers via metal ion linkages has become an important strategy for interfacial engineering of metalloid and metal oxide (MOx) substrates, with applications in numerous areas, including energy harvesting, catalysis, and chemical sensing. An important aspect for the rational design of these multilayers is knowledge of the molecular structure-function relationships. For example, in a multilayer composed of different chromophores in each layer, the molecular orientation of each layer, both relative to the adjacent layers and the substrate, influences the efficiency of vectorial energy and electron transfer. Here, we describe an approach using UV-vis attenuated total reflection (ATR) spectroscopy to determine the mean dipole tilt angle of chromophores in each layer in a metal ion-linked trilayer self-assembled on indium-tin oxide. To our knowledge, this is the first report demonstrating the measurement of the orientation of three different chromophores in a single assembly. The ATR approach allows the adsorption of each layer to be monitored in real-time, and any changes in the orientation of an underlying layer arising from the adsorption of an overlying layer can be detected. We also performed transient absorption spectroscopy to monitor interlayer energy transfer dynamics in order to relate structure to function. We found that near unity efficiency, sub-nanosecond energy transfer between the third and second layer was primarily dictated by the distance between the chromophores. Thus, in this case, the orientation had minimal impact at such proximity.

Influence of Al2O3 Overlayers on Intermolecular Interactions between Metal Oxide Bound Molecules.

Intermolecular interactions on inorganic substrates can have a critical impact on the electrochemical and photophysical properties of the materials and subsequent performance in hybrid electronics. Critical to the intentional formation or inhibition of these processes is controlling interactions between molecules on a surface. In this report, we investigated the impact of surface loading and atomic-layer-deposited Al2O3 overlayers on the intermolecular interactions of a ZrO2-bound anthracene derivative as probed by the photophysical properties of the interface. While surface loading density had no impact on the absorption spectra of the films, there was an increase in excimer features with surface loading as observed by both emission and transient absorption. The addition of ALD overlayers of Al2O3 resulted in a decrease in excimer formation, but the emission and transient absorption spectra were still dominated by excimer features. These results suggest that ALD may provide a post-surface loading means of influencing such intermolecular interactions.

Antiferroelectric Phase Transition in a Proton-Transfer Salt of Squaric Acid and 2,3-Dimethylpyrazine.

A proton-transfer reaction between squaric acid (H2sq) and 2,3-dimethylpyrazine (2,3-Me2pyz) results in crystallization of a new organic antiferroelectric (AFE), (2,3-Me2pyzH+)(Hsq-)·H2O (1), which possesses a layered structure. The structure of each layer can be described as partitioned into strips lined with methyl groups of the Me2pyzH+ cations and strips featuring extensive hydrogen bonding between the Hsq- anions and water molecules. Variable-temperature dielectric measurements and crystal structures determined through a combination of single-crystal X-ray and neutron diffraction reveal an AFE ordering at 104 K. The phase transition is driven by ordering of protons within the hydrogen-bonded strips. Considering the extent of proton transfer, the paraelectric (PE) state can be formulated as (2,3-Me2pyzH+)2(Hsq23-)(H5O2+), whereas the AFE phase can be described as (2,3-Me2pyzH+)(Hsq-)(H2O). The structural transition caused by the localization of protons results in the change in color from yellow in the PE state to colorless in the AFE state. The occurrence and mechanism of the AFE phase transition have been also confirmed by heat capacity measurements and variable-temperature infrared and Raman spectroscopy. This work demonstrates a potentially promising approach to the design of new electrically ordered materials by engineering molecule-based crystal structures in which hydrogen-bonding interactions are intentionally partitioned into quasi-one-dimensional regions.

Molecular Orientation of -PO3H2 and -COOH Functionalized Dyes on TiO2, Al2O3, ZrO2, and ITO: A Comparative Study.

Modification of transparent metal oxide (MOx) surfaces with organic monolayers is widely employed to tailor the properties of interfaces in organic electronic devices, and MOx substrates modified with light-absorbing chromophores are a key component of dye-sensitized solar cells (DSSCs). The effects of an organic modifier on the performance of a MOx-based device are frequently assessed by performing experiments on model monolayer|MOx interfaces, where an "inert" MOx (e.g., Al2O3) is used as a control for an "active" MOx (e.g., TiO2). An underlying assumption in these studies is that the structure of the MOx-monolayer complex is similar between different metal oxides. The validity of this assumption was examined in the present study. Using UV-Vis attenuated total reflection spectroscopy, we measured the mean dipole tilt angle of 4,4'-(anthracene-9,10-diyl)bis(4,1-phenylene)diphosphonic acid (A1P) adsorbed on indium tin oxide (ITO), TiO2, ZrO2, and Al2O3. When the surface roughness of the MOx substrate and the surface coverage (𝛤) of the A1P film were constant, the molecular orientation of A1P was the same on these substrates. The study was extended to 4,4'-(anthracene-9,10-diyl)bis(4,1-phenylene)dicarboxylic acid (A1C) adsorbed on the same group of MOx substrates. The mean tilt angle of A1C and A1P films on ITO was the same, which is likely due the intermolecular interactions resulting from the high and approximately equal 𝛤 of both films. Comparing A1C films at the same 𝛤 on TiO2 and Al2O3 having the same surface roughness, there was no difference in the mean tilt angle. MD simulations of A1C and A1P on TiO2 produced nearly identical tilt angle distributions, which supports the experimental findings. This study provides first experimental support for the assumption that the structure of the MOx-modifer film is the same on an "active" substrate vs. a "inert" control substrate.

Efficient Route for the Preparation of Composite Resin Incorporating Silver Nanoparticles with Enhanced Antibacterial Properties.

An efficient and facile route for the immobilization of silver (Ag) nanoparticles (NPs) in anion exchange resin beads with different silver loading is proposed. In this method, BH4- ions were first introduced into chloride-form resin through an ion exchange process with Cl- ions, followed by in-situ chemical reduction of Ag+ ions at the surface of the resin to form metallic Ag nanoparticles. Morphology and structure of the resulting Ag-resin nanocomposites were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive spectroscopy (EDS), Fourier transform infra-red (FTIR), inductively coupled plasma-optical emission spectrometry (ICP-OES), and thermogravimetry analysis (TGA). The results confirmed the presence of smaller diameter Ag NPs incorporated into the resin beads having an average diameter on the order of 10 nm with a few Ag NP clusters of 20-100 nm. The nanoparticles were homogeneously distributed throughout the resin. There were no dramatic increases in average particle sizes even at very high Ag loadings. The resin retained its structure and stability, allowing higher stability of immobilized AgNPs than the colloidal ones. The Ag-loaded resins made with 50 mM AgNO3 were tested for antibacterial activity in vitro against Escherichia coli (E. coli) as a model microbial contaminant in water. Results showed greater than 99% bacterial inhibition within 3 h of exposure. The resin form offers greater ease of handling, long-term storage at room temperature, reusability in repeated reactions, and reduces the risk of environmental contamination.

Harnessing Sunlight via Molecular Photon Upconversion.

Molecular photon upconversion via triplet-triplet annihilation (TTA-UC) is an intriguing strategy to harness sub-bandgap photons and surpass the Shockley-Queisser (SQ) limit for solar energy conversion. In this perspective, we briefly summarize the progress to date harnessing TTA-UC in solar cells using both optically and electrically coupled schemes. We then highlight the efficiency limiting processes for these schemes and outline possible paths toward upconverted photocurrent contributions of >1 mA/cm2. Further progress in red-shifting absorption, coupling to high-energy light harvesting motifs, photon management, sensitizer/annihilator design, and more are necessary for the realization of a viable TTA-UC solar cell that can pass the SQ limit.

Hollow metal halide perovskite nanocrystals with efficient blue emissions.

Metal halide perovskite nanocrystals (NCs) have emerged as new-generation light-emitting materials with narrow emissions and high photoluminescence quantum efficiencies (PLQEs). Various types of perovskite NCs, e.g., platelets, wires, and cubes, have been discovered to exhibit tunable emissions across the whole visible spectrum. Despite remarkable advances in the field of perovskite NCs, many nanostructures in inorganic NCs have not yet been realized in metal halide perovskites, and producing highly efficient blue-emitting perovskite NCs remains challenging and of great interest. Here, we report the discovery of highly efficient blue-emitting cesium lead bromide (CsPbBr3) perovskite hollow NCs. By facile solution processing of CsPbBr3 precursor solution containing ethylenediammonium bromide and sodium bromide, in situ formation of hollow CsPbBr3 NCs with controlled particle and pore sizes is realized. Synthetic control of hollow nanostructures with quantum confinement effect results in color tuning of CsPbBr3 NCs from green to blue, with high PLQEs of up to 81%.

Suppressed phase separation of mixed-halide perovskites confined in endotaxial matrices.

The functionality and performance of a semiconductor is determined by its bandgap. Alloying, as for instance in InxGa1-xN, has been a mainstream strategy for tuning the bandgap. Keeping the semiconductor alloys in the miscibility gap (being homogeneous), however, is non-trivial. This challenge is now being extended to halide perovskites - an emerging class of photovoltaic materials. While the bandgap can be conveniently tuned by mixing different halogen ions, as in CsPb(BrxI1-x)3, the so-called mixed-halide perovskites suffer from severe phase separation under illumination. Here, we discover that such phase separation can be highly suppressed by embedding nanocrystals of mixed-halide perovskites in an endotaxial matrix. The tuned bandgap remains remarkably stable under extremely intensive illumination. The agreement between the experiments and a nucleation model suggests that the size of the nanocrystals and the host-guest interfaces are critical for the photo-stability. The stabilized bandgap will be essential for the development of perovskite-based optoelectronics, such as tandem solar cells and full-color LEDs.