Balancing Activity and Stability through Compositional Engineering of Ternary PtNi-Au Alloy ORR Catalysts.

Achieving the optimal balance between cost-efficiency and stability of oxygen reduction reaction (ORR) catalysts is currently among the key research focuses aiming at reaching a broader implementation of proton-exchange membrane fuel cells (PEMFCs). To address this challenge, we combine two well-established strategies to enhance both activity and stability of platinum-based ORR catalysts. Specifically, we prepare ternary PtNi-Au alloys, where each alloying element plays a distinct role: Ni reduces costs and boosts ORR activity, while Au enhances stability.

Enantiomorphic single component conducting nickel(II) and platinum(II) bis(diethyl-dddt) crystalline complexes.

Monoanionic and neutral nickel(II) and platinum(II) bis(dithiolene) complexes based on the 5,6-diethyl-5,6-dihydro-1,4-dithiin-2,3-dithiolate (de-dddt) chiral ligand have been prepared in racemic and enantiopure forms. Neutral closed-shell species have been generated from monoanionic precursors upon electrocrystallization. The racemic anionic (TBA)[Ni(,-de-dddt)(,-de-dddt)] complex crystallized in the centrosymmetric space group 2/, while the neutral complexes crystallized in the enantiomorphic tetragonal space group 422 or 422.

Electronic and Structural Properties of Thin Iron Oxide Films on CeO.

Modification of CeO (ceria) with 3d transition metals, particularly iron, has been proven to significantly enhance its catalytic efficiency in oxidation or combustion reactions. Although this phenomenon is widely reported, the nature of the iron-ceria interaction responsible for this improvement remains debated. To address this issue, we prepared well-defined model FeO/CeO(111) catalytic systems and studied their structure and interfacial electronic properties using photoelectron spectroscopy, scanning tunneling microscopy, and low-energy electron diffraction, coupled with density functional theory (DFT) calculations.

Chemical Orderings in CuCo Nanoparticles: Topological Modeling Using DFT Calculations.

The orderings of atoms in bimetallic 1.6-2.1 nm-large CuCo nanoparticles, important as catalytic and magnetic materials, were studied using a combination of DFT calculations with a topological approach.

Mixed-ligand, radical, gold bis(dithiolene) complexes: from single-component conductors to controllable NIR-II absorbers.

Neutral radical bis(dithiolene) gold complexes [Au(dt)]˙ are known to exhibit a strong absorption in the 1400-2000 nm NIR absorption range. Here, we demonstrate that the NIR signature of mixed-ligand bis(dithiolene) gold complexes [Au(dt)(dt)]˙ associating two different dithiolene, dt and dt, is found at higher energy, out of the range of the homoleptic analogs [Au(dt)]˙ and [Au(dt)]˙, in the looked-after NIR-II 1000-1400 nm absorption range. An efficient synthetic approach towards precursor mixed-ligand monoanionic gold bis(dithiolene) complexes [Au(dt)(dt)] is reported.

Enhancing c-Si Solar Cell Efficiency in the UV Region: Photophysical Insights into the Use of Eu Complexes for Down-Shifting Layer Applications.

[Eu(DPIQC)] (where DPIQC = 3-(diphenyl phosphoryl)-1-isoquinolinecarboxylate), a luminescent europium complex with antenna ligands, has been carefully embedded within a polyvinyl butyral (PVB) matrix and the resulting material was used to prepare films used as luminescent down-shifting layers (LDSLs) for crystalline Si-based solar cells. The films were characterized using photoluminescence spectroscopy, atomic force spectroscopy (AFM), UV-Vis spectroscopy, and fluorescence microscopy. The AFM analysis shows films with low surface roughness, while fluorescence microscopy revealed that the Eu complex embedded in PVB assumed a spheroidal configuration, a morphology especially beneficial for optical applications.

Mixed-Valence Conductors from Ni Bis(diselenolene) Complexes with a Thiazoline Backbone.

Highly conducting, mixed-valence, multi-component nickel bis() salts were obtained by electrocrystallization of the monoanionic species [Ni(Me-thiazds)] (Me-thiazds: -methyl-1,3-thiazoline-2-thione-4,5-diselenolate), with 1:2 and 1:3 stoichiometries depending of the counter ion used (EtN and BuN PhP, respectively). This behavior strongly differs from that of the corresponding monoanionic complexes whose oxidation afforded the single component neutral species. This provides additional rare examples of mixed-valence conducting salts of nickel diselenolene complexes, only known in two examples with the dsit (1,3-dithiole-2-thione-4,5-diselenolate) and dsise (1,3-dithiole-2-selone-4,5-diselenolate) ligands.

Bis(Vinylenedithio)-Tetrathiafulvalene-Based Coordination Networks.

Novel coordination polymers embedding electroactive moieties present a high interest in the development of porous conducting materials. While tetrathiafulvalene (TTF) based metal-organic frameworks were reported to yield through-space conducting frameworks, the use of S-enriched scaffolds remains elusive in this field. Herein is reported the employment of bis(vinylenedithio)-tetrathiafulvalene (BVDT-TTF) functionalized with pyridine coordinating moieties in coordination polymers.

Intermolecular Resonance Correlates Electron Pairs Down a Supermolecular Chain: Antiferromagnetism in K-Doped -Terphenyl.

Recent interest in potassium-doped -terphenyl has been fueled by reports of superconductivity at values surprisingly high for organic compounds. Despite these interesting properties, studies of the structure-function relationships within these materials have been scarce. Here, we isolate a phase-pure crystal of potassium-doped -terphenyl: [K()][-terphenyl].

Crystallization Induced Enhanced Emission in Two New Zn(II) and Cd(II) Supramolecular Coordination Complexes with the 1-(3,4-Dimethylphenyl)-5-Methyl-1-1,2,3-Triazole-4-Carboxylate Ligand.

Two new metal supramolecular metal-organic frameworks (SMOFs) with general formula [ML(HO)] (M = Zn, Cd) have been synthetized using the sodium salt of the anionic 1-(3,4-dimethylphenyl)-5-methyl-1H-1,2,3-triazole-4-carboxylate ligand (NaL). Both SMOFs have been structurally characterized by single-crystal X-ray diffraction analysis and IR spectroscopy. The compounds are isostructural and form supramolecular aggregates via hydrogen bonds with the presence of less common dihydrogen bonds.

In Search of Chiral Molecular Superconductors: κ-[(S,S)-DM-BEDT-TTF] ClO Revisited.

The relationship between chirality and superconductivity is an intriguing question. The two enantiomeric crystalline radical cation salts κ-[(S,S)-DM-BEDT-TTF] ClO and κ-[(R,R)-DM-BEDT-TTF] ClO , showing κ-type arrangement of the organic layers, are investigated in search for superconducting chiral molecular materials following a 1992 report indicating the occurrence of a superconducting transition in the former compound. While the initial interpretation is presently challenged through in-depth temperature and pressure dependent single crystal resistivity measurements combined with band structure calculations, the two chiral conductors show metal like behavior with room temperature conductivities of 10-30 S cm at ambient pressure and stabilization of the metallic state down to the lowest temperatures under moderate pressures.

Engineering Polar Oxynitrides: Hexagonal Perovskite BaWON.

Non-centrosymmetric polar compounds have important technological properties. Reported perovskite oxynitrides show centrosymmetric structures, and for some of them high permittivities have been observed and ascribed to local dipoles induced by partial order of nitride and oxide. Reported here is the first hexagonal perovskite oxynitride BaWON , which shows a polar 6H polytype.

Electronic engineering of a tetrathiafulvalene charge-transfer salt via reduced symmetry induced by combined substituents.

A 1 : 1 metallic charge-transfer salt is obtained by cosublimation of (Z,E)-(SMe)2Me2TTF and TCNQ. X-ray diffraction studies confirm the formation of segregated stacks comprising donor and acceptor molecules in [(E)-(SMe)2Me2TTF](TCNQ). The crystal packing features lateral SS interactions between TTF stacks, which is in sharp contrast to that in (TTF)(TCNQ).

Conformational analysis of enantiomerization coupled to internal rotation in triptycyl-n-helicenes.

We present a computational study of a reduced potential energy surface (PES) to describe enantiomerization and internal rotation in three triptycyl-n-helicene molecules, centering the discussion on the issue of a proper reaction coordinate choice. To reflect the full symmetry of both strongly coupled enantiomerization and rotation processes, two non-fixed combinations of dihedral angles must be used, implying serious computational problems that required the development of a complex general algorithm. The characteristic points on each PES are analyzed, the intrinsic reaction coordinates are calculated, and finally they are projected on the reduced PES.

Charge Delocalization, Oxidation States, and Silver Mobility in the Mixed Silver-Copper Oxide AgCuO ¤.

The electronic structure of AgCuO, and more specifically the possible charge delocalization and its implications for the transport properties, has been the object of debate. Here the problem is faced by means of first-principles density functional theory calculations of the electron and phonon band structures as well as molecular dynamics simulations for different temperatures. It is found that both Cu and Ag exhibit noninteger oxidation states, in agreement with previous spectroscopic studies.

Conducting Anilate-Based Mixed-Valence Fe(II)Fe(III) Coordination Polymer: Small-Polaron Hopping Model for Oxalate-Type Fe(II)Fe(III) 2D Networks.

The mixed-valence FeFe 2D coordination polymer formulated as [TAG][FeFe(ClCNAn)]·(solvate) 1 (TAG = tris(amino)-guanidinium, ClCNAn = chlorocyanoanilate dianionic ligand) crystallized in the polar trigonal space group P3. In the solid-state structure, determined both at 150 and at 10 K, anionic 2D honeycomb layers [FeFe(ClCNAn)] establish in the ab plane, with an intralayer metal-metal distance of 7.860 Å, alternating with cationic layers of TAG.

Effects of Temperature on the Shape and Symmetry of Molecules and Solids.

Despite its undeniable problems from a philosophical point of view, the concept of molecular structure, with attributes such as shape and symmetry, directly borrowed from the description of macroscopic objects, is nowadays central to most of the chemical sciences. Descriptions such as "the tetrahedral carbon atom" or "octahedral coordination complexes" are widely used as much in elementary textbooks as in the most up-to-date research articles. The definition of molecular shape is, however, not as simple as it might seem at first sight.

Evaluation of novel platinum(ii) based AIE compound-encapsulated mesoporous silica nanoparticles for cancer theranostic application.

Advanced biomedical research has established that cancer is a multifactorial disorder which is highly heterogeneous in nature and responds differently to different treatment modalities, due to which constant monitoring of therapy response is becoming extremely important. To accomplish this, different theranostic formulations have been evaluated. However, most of them are found to suffer from several limitations extending from poor resolution, radiation damage, to high costs.

Localization versus Delocalization in Chiral Single Component Conductors of Gold Bis(dithiolene) Complexes.

The first examples of chiral single component conductors are reported. Both (S,S) and (R,R) enantiomers of 5,6-dimethyl-5,6-dihydro-1,4-dithiin-2,3-dithiolate (dm-dddt) ligand have been used to prepare anionic metal bis(dithiolene) complexes formulated as ([(n-Bu)4N][M(dm-dddt)2] (M = Au, Ni), which are isostructural according to single crystal X-ray analysis. Single crystal transport measurements indicate semiconducting behavior for the anionic radical Ni complexes, with low room temperature conductivity values and high activation energies.

Self-Assembly of Discrete Metallocycles Coordination Polymers Based on Cu(I) and Ag(I) Ions and Flexible Ligands: Structural Diversification and Luminescent Properties.

Three new Ag(I) and one Cu(I) coordination compounds with two different positional isomers, propane-1,3-diyl bis(pyridine-4-carboxylate) (L1) and propane-1,3-diyl bis(pyridine-3-carboxylate) (L2), of a bis-(pyridyl-carboxylate) ligand have been synthesized. X-ray diffraction analysis revealed that the self-assembly of L1 with AgCF₃SO₃ and AgClO₄ salts leads to the formation of discrete binuclear metallocycles {Ag(L1)CF₃SO₃}₂ () and {Ag(L1)ClO₄}₂ (), respectively. However, self-assembly of the other ligand, L2, with AgCF₃SO₃ and CuCl salts, results in a 1-D zig-zag chain {Ag(L2)CF₃SO₃} () and a 1-D double-stranded helical chain {Cu₂Cl₂(L2)₂} () coordination polymers, respectively.

Structural and electronic control of the metal to insulator transition and local orderings in the θ-(BEDT-TTF)2X organic conductors.

A first-principles density functional theory (DFT) study of [Formula: see text]-(BEDT-TTF)2X molecular conductors with X  =  I3, CsCo(SCN)4 (ambient pressure, 7.5 kbar and 10 kbar), CsZn(SCN)4, TlCo(SCN)4, RbCo(SCN)4 and RbZn(SCN)4 (220 K and 90 K) is reported. It is shown that these salts exhibit three different types of band structure each of them associated with a different physical behavior.

Links between the Crystal and Electronic Structure in the New Family of Unconventional Superconductors A2Cr3As3 (A = K, Rb, Cs).

The electronic structure of a new family of superconductors is examined through density functional theory calculations. In contrast with other quasi-1D superconductors, these phases exhibit a relatively complex electronic structure and the Fermi surface contains both 1D and 3D components. It is shown that cations have an almost nil influence on the electronic structure.

Electronic Structure and Magnetic Properties of CuFeS2.

Chalcopyrite (CuFeS2) is an antiferromagnetic semiconductor with unusual magnetic and electrical properties, which are still not clearly understood. Neutron diffraction experiments reveal a phase transition at ∼50 K that has been attributed to an unexpected appearance of magnetic moments on Cu ions, having a paramagnetic arrangement down to 50 K and then ordering to an antiferromagnetic state at lower temperatures. In this study we use DFT-based computational methods to investigate the electronic structure and magnetic properties of CuFeS2 in order to obtain a reliable source of information for the interpretation of the observed magnetic behavior, and in particular to shed some light on the magnetic behavior of copper atoms in this compound.

Exploring the electronic structure of an organic semiconductor based on a compactly fused electron donor-acceptor molecule.

A Mott-type semiconductor based on a compactly fused and partially oxidized electron donor-acceptor (D-A) molecule was recently prepared and identified to exhibit a large room-temperature conductivity of 2 S cm(-1) . In a marked contrast to the organic conductors characterized by relatively well decoupled and segregated uniform stacks of D and A moieties, the formally half-oxidized tetrathiafulvalene donors of the actual compound are organized in columnar π stacks only, whereby the coplanar electron-acceptor units, namely benzothiadiazole, are closely annulated along their ridges. Herein, we present a theoretical study that explores the electronic structure of this novel type of organic semiconductor.