Metal–metal bonded alkaline-earth distannyls

The first families of alkaline-earth stannylides [Ae(SnPh₃)₂·(thf)_x] (Ae = Ca, x = 3, 1; Sr, x = 3, 2; Ba, x = 4, 3) and [Ae{Sn(SiMe₃)₃}₂·(thf)_x] (Ae = Ca, x = 4, 4; Sr, x = 4, 5; Ba, x = 4, 6), where Ae is a large alkaline earth with direct Ae–Sn bonds, are presented. All complexes have been characterised by high-resolution solution NMR spectroscopy, including ¹¹⁹Sn NMR, and by X-ray diffraction crystallography. The molecular structures of [Ca(SnPh₃)₂·(thf)₄] (1′), [Sr(SnPh₃)₂·(thf)₄] (2′), [Ba(SnPh₃)₂·(thf)₅] (3′), 4, 5 and [Ba{Sn(SiMe₃)₃}₂·(thf)₅] (6′), most of which crystallised as higher thf solvates than their parents 1–6, were established by XRD analysis; the experimentally determined Sn–Ae–Sn′ angles lie in the range 158.10(3)–179.33(4)°. In a given series, the ¹¹⁹Sn NMR chemical shifts are slightly deshielded upon descending group 2 from Ca to Ba, while the silyl-substituted stannyls are much more shielded than the phenyl ones (δ¹¹⁹Sn/ppm: 1′, −133.4; 2′, −123.6; 3′, −95.5; 4, −856.8; 5, −848.2; 6′, −792.7). The bonding and electronic properties of these complexes were also analysed by DFT calculations. The combined spectroscopic, crystallographic and computational analysis of these complexes provide some insight into the main features of these unique families of homoleptic complexes. A comprehensive DFT study (Wiberg bond index, QTAIM and energy decomposition analysis) points at a primarily ionic Ae–Sn bonding, with a small covalent contribution, in these series of complexes; the Sn–Ae–Sn′ angle is associated with a flat energy potential surface around its minimum, consistent with the broad range of values determined by experimental and computational methods.

The complete series of heterobimetallic alkaline-earth distannyls [Ae{SnR₃}₂·(thf)_x] (Ae = Ca, Sr, Ba) have been prepared for R = Ph and SiMe₃, and their bonding and electronic properties have been comprehensively investigated.     

Structural Characterization of Cis– and Trans–Pt(NH3)2Cl2 Conjugations with Chitosan Nanoparticles

The conjugation of chitosan 15 and 100 KD with anticancer drugs cis– and trans–Pt (NH₃)₂Cl₂ (abbreviated cis–Pt and trans–Pt) were studied at pH 5–6. Using multiple spectroscopic methods and thermodynamic analysis to characterize the nature of drug–chitosan interactions and the potential application of chitosan nanoparticles in drug delivery. Analysis showed that both hydrophobic and hydrophilic contacts are involved in drug–polymer interactions, while chitosan size and charge play a major role in the stability of drug–polymer complexes. The overall binding constants are K_{ch–15–cis–Pt} = 1.44 (±0.6) × 10⁵ M⁻¹, K_{ch–100–cis–Pt} = 1.89 (±0.9) × 10⁵ M⁻¹ and K_{ch–15–trans–Pt} = 9.84 (±0.5) × 10⁴ M⁻¹, and K_{ch–100–trans–Pt} = 1.15 (±0.6) × 10⁵ M⁻¹. More stable complexes were formed with cis–Pt than with trans–Pt–chitosan adducts, while stronger binding was observed for chitosan 100 in comparison to chitosan 15 KD. This study indicates that polymer chitosan 100 is a stronger drug carrier than chitosan 15 KD in vitro.     

Ir6In32S21, a polar,metal-rich semiconducting subchalcogenide

Subchalcogenides are uncommon, and their chemical bonding results from an interplay between metal–metal and metal–chalcogenide interactions. Herein, we present Ir₆In₃₂S₂₁, a novel semiconducting subchalcogenide compound that crystallizes in a new structure type in the polar P31m space group, with unit cell parameters a = 13.9378(12) Å, c = 8.2316(8) Å, α = β = 90°, γ = 120°. The compound has a large band gap of 1.48(2) eV, and photoemission and Kelvin probe measurements corroborate this semiconducting behavior with a valence band maximum (VBM) of −4.95(5) eV, conduction band minimum of −3.47(5) eV, and a photoresponse shift of the Fermi level by ∼0.2 eV in the presence of white light. X-ray absorption spectroscopy shows absorption edges for In and Ir do not indicate clear oxidation states, suggesting that the numerous coordination environments of Ir₆In₃₂S₂₁ make such assignments ambiguous. Electronic structure calculations confirm the semiconducting character with a nearly direct band gap, and electron localization function (ELF) analysis suggests that the origin of the gap is the result of electron transfer from the In atoms to the S 3p and Ir 5d orbitals. DFT calculations indicate that the average hole effective masses near the VBM (1.19m_e) are substantially smaller than the average electron masses near the CBM (2.51m_e), an unusual feature for most semiconductors. The crystal and electronic structure of Ir₆In₃₂S₂₁, along with spectroscopic data, suggest that it is neither a true intermetallic nor a classical semiconductor, but somewhere in between those two extremes.

Subchalcogenides are uncommon, and their chemical bonding results from an interplay between metal–metal and metal–chalcogenide interactions.     

Computational Studies of Coinage Metal Anion M− + CH3X (X = F,Cl, Br,I) Reactions in Gas Phase

We characterized the stationary points along the nucleophilic substitution (S_N2), oxidative insertion (OI), halogen abstraction (XA), and proton transfer (PT) product channels of M⁻ + CH₃X (M = Cu, Ag, Au; X = F, Cl, Br, I) reactions using the CCSD(T)/aug-cc-pVTZ level of theory. In general, the reaction energies follow the order of PT > XA > S_N2 > OI. The OI channel that results in oxidative insertion complex [CH₃–M–X]⁻ is most exothermic, and can be formed through a front-side attack of M on the C-X bond via a high transition state OxTS or through a S_N2-mediated halogen rearrangement path via a much lower transition state invTS. The order of OxTS > invTS is inverted when changing M⁻ to Pd, a d¹⁰ metal, because the symmetry of their HOMO orbital is different. The back-side attack S_N2 pathway proceeds via typical Walden-inversion transition state that connects to pre- and post-reaction complexes. For X = Cl/Br/I, the invS_N2-TS’s are, in general, submerged. The shape of this M⁻ + CH₃X S_N2 PES is flatter as compared to that of a main-group base like F⁻ + CH₃X, whose PES has a double-well shape. When X = Br/I, a linear halogen-bonded complex [CH₃−X∙··M]⁻ can be formed as an intermediate upon the front-side attachment of M on the halogen atom X, and it either dissociates to CH₃ + MX⁻ through halogen abstraction or bends the C-X-M angle to continue the back-side S_N2 path. Natural bond orbital analysis shows a polar covalent M−X bond is formed within oxidative insertion complex [CH₃–M–X]⁻, whereas a noncovalent M–X halogen-bond interaction exists for the [CH₃–X∙··M]⁻ complex. This work explores competing channels of the M⁻ + CH₃X reaction in the gas phase and the potential energy surface is useful in understanding the dynamic behavior of the title and analogous reactions.     

Magnesium–halobenzene bonding: mapping the halogen sigma-hole with a Lewis-acidic complex

Complexes of the Lewis base-free cations (^MeBDI)Mg⁺ and (^tBuBDI)Mg⁺ with Ph–X ligands (X = F, Cl, Br, I) have been studied (^MeBDI = HC[C(Me)N-DIPP]₂ and ^tBuBDI = HC[C(tBu)N-DIPP]₂; DIPP = 2,6-diisopropylphenyl). For the smaller β-diketiminate ligand (^MeBDI) only complexes with PhF could be isolated. Heavier Ph–X ligands could not compete with bonding of Mg to the weakly coordinating anion B(C₆F₅)₄⁻. For the cations with the bulkier ^tBuBDI ligand, the full series of halobenzene complexes was structurally characterized. Crystal structures show that the Mg⋯X–Ph angle strongly decreases with the size of X: F 139.1°, Cl 101.4°, Br 97.7°, I 95.1°. This trend, which is supported by DFT calculations, can be explained with the σ-hole which increases from F to I. Charge calculation and Atoms-In-Molecules analyses show that Mg⋯F–Ph bonding originates from electrostatic attraction between Mg²⁺ and the very polar C^δ+–F^δ− bond. For the heavier halobenzenes, polarization of the halogen atom becomes increasingly important (Cl < Br < I). Complexation with Mg leads in all cases to significant Ph–X bond activation and elongation. This unusual coordination of halogenated species to early main group metals is therefore relevant to C–X bond breaking.

Complexes of a highly Lewis acidic Mg cation and the full series of Ph–X (X = F, Cl, Br, I) have been structurally characterized. The Mg⋯X–Ph angle decreases with halogen size on account of the growing halogen σ-hole.     

Heterometallic Europium(III)–Lutetium(III) Terephthalates as Bright Luminescent Antenna MOFs

A new series of luminescent heterometallic europium(III)–lutetium(III) terephthalate metal–organic frameworks, namely (Eu_xLu_1−x)₂bdc₃·nH₂O, was synthesized using a direct reaction in a water solution. At the Eu³⁺ concentration of 1–40 at %, the MOFs were formed as a binary mixture of the (Eu_xLu_1−x)₂bdc₃ and (Eu_xLu_1−x)₂bdc₃·4H₂O crystalline phases, where the Ln₂bdc₃·4H₂O crystalline phase was enriched by europium(III) ions. At an Eu³⁺ concentration of more than 40 at %, only one crystalline phase was formed: (Eu_xLu_1−x)₂bdc₃·4H₂O. All MOFs containing Eu³⁺ exhibited sensitization of bright Eu³⁺-centered luminescence upon the 280 nm excitation into a ¹ππ* excited state of the terephthalate ion. The fine structure of the emission spectra of Eu^{3+ 5}D₀-⁷F_J (J = 0–4) significantly depended on the Eu³⁺ concentration. The luminescence quantum yield of Eu³⁺ was significantly larger for Eu-Lu terephthalates containing a low concentration of Eu³⁺ due to the absence of Eu-Eu energy migration and the presence of the Ln₂bdc₃ crystalline phase with a significantly smaller nonradiative decay rate compared to the Ln₂bdc₃·4H₂O.     

Dielectric Properties Investigation of Metal–Insulator–Metal (MIM) Capacitors

This study presents the construction and dielectric properties investigation of atomic-layer-deposition Al₂O₃/TiO₂/HfO₂ dielectric-film-based metal–insulator–metal (MIM) capacitors. The influence of the dielectric layer material and thickness on the performance of MIM capacitors are also systematically investigated. The morphology and surface roughness of dielectric films for different materials and thicknesses are analyzed via atomic force microscopy (AFM). Among them, the 25 nm Al₂O₃-based dielectric capacitor exhibits superior comprehensive electrical performance, including a high capacitance density of 7.89 fF·µm⁻², desirable breakdown voltage and leakage current of about 12 V and 1.4 × 10⁻¹⁰ A·cm⁻², and quadratic voltage coefficient of 303.6 ppm·V⁻². Simultaneously, the fabricated capacitor indicates desirable stability in terms of frequency and bias voltage (at 1 MHz), with the corresponding slight capacitance density variation of about 0.52 fF·µm⁻² and 0.25 fF·µm⁻². Furthermore, the mechanism of the variation in capacitance density and leakage current might be attributed to the Poole–Frenkel emission and charge-trapping effect of the high-k materials. All these results indicate potential applications in integrated passive devices.     

The Influence of the Halide in the Crystal Structures of 1-(2,3,5,6-Tetrafluoro-4-pyridyl)-3-benzylimidazolium Halides

The crystal structures of 1-(2,3,5,6-tetrafluoro-4-pyridyl)-3-benzylimidazolium chloride (1) and iodide (3) have been determined by single crystal X-ray diffraction. The crystal structure of 1 is similar to that of the bromide salt (2), possessing anion···C₅F₅N···C₆H₅ motifs, whilst that of 3 contains columns of alternating iodide anions and parallel tetrafluoropyridyl rings. All three crystal structures possess C(1)–H∙∙∙X⁻ and C(2)–H∙∙∙X⁻ hydrogen bonding. DFT calculations reveal that the strengths of the hydrogen bonding interactions lie in the order C(1)–H···X⁻ > C(3)–H···X⁻ > C(2)–H···X⁻ for the same halide (X⁻) and Cl⁻ > Br⁻ > I⁻ for each position. It is suggested that salt 3 adopts a different structure to salts 1 and 2 because of the larger size of iodide.     

Ion polarisation-assisted hydrogen-bonded ferroelectrics in liquid crystalline domains

An alkylamide-substituted (−NHCOC₁₀H₂₁) hydrogen-bonded dibenzo[18]crown-6 derivative (1) was prepared to stabilise the ionic channel structure in a discotic hexagonal columnar (Col_h) liquid crystal. The introduction of simple M⁺X⁻ salts such as Na⁺PF₆⁻ and K⁺I⁻ into the ionic channel of 1 enhanced the ionic conductivity of the Col_h phase of the M⁺·(1)·X⁻ salts, with the highest ionic conductivity reaching ∼10⁻⁶ S cm⁻¹ for K⁺·(1)·I⁻ and Na⁺·(1)·PF₆⁻ at 460 K, which was approximately 5 orders of magnitude higher than that of 1. The introduction of non-ferroelectric 1 into the ferroelectric N,N′,N′′-tri(tetradecyl)-1,3,5-benzenetricarboxamide (3BC) elicited a ferroelectric response from the mixed Col_h phase of (3BC)_x(1)_1−x with x = 0.9 and 0.8. The further doping of M⁺X⁻ into the ferroelectric Col_h phase of (3BC)_0.9(1)_0.1 enhanced the ferroelectric polarisation assisted by ion displacement in the half-filled ionic channel for the vacant dibenzo[18]crown-6 of (3BC)_0.9[(M⁺)_0.5·(1)·(X⁻)_0.5]_0.1.

An alkylamide-substituted (−NHCOC₁₀H₂₁) hydrogen-bonded dibenzo[18]crown-6 derivative (1) was prepared to stabilise the ionic channel structure in a discotic hexagonal columnar (Col_h) liquid crystal.     

Tuning of bandgaps and emission properties of light-emitting diode materials through homogeneous alloying in molecular crystals

Alloy formation is ubiquitous in inorganic materials science, and it strongly depends on the similarity between the alloyed atoms. Since molecules have widely different shapes, sizes and bonding properties, it is highly challenging to make alloyed molecular crystals. Here we report the generation of homogenous molecular alloys of organic light emitting diode materials that leads to tuning in their bandgaps and fluorescence emission. Tris(8-hydroxyquinolinato)aluminium (Alq₃) and its Ga, In and Cr analogues (Gaq₃, Inq₃, and Crq₃) form homogeneous mixed crystal phases thereby resulting in binary, ternary and even quaternary molecular alloys. The M_xM′_(1−x)q₃ alloy crystals are investigated using X-ray diffraction, energy dispersive X-ray spectroscopy and Raman spectroscopy on single crystal samples, and photoluminescence properties are measured on the exact same single crystal specimens. The different series of alloys exhibit distinct trends in their optical bandgaps compared with their parent crystals. In the Al_xGa_(1−x)q₃ alloys the emission wavelengths lie in between those of the parent crystals, while the Al_xIn_(1−x)q₃ and Ga_xIn_(1−x)q₃ alloys have red shifts. Intriguingly, efficient fluorescence quenching is observed for the M_xCr_(1−x)q₃ alloys (M = Al, Ga) revealing the effect of paramagnetic molecular doping, and corroborating the molecular scale phase homogeneity.

Multicomponent molecular alloy crystals exhibit intriguing effects of tuning and quenching in their photoluminescence, suggesting ‘alloy-crystal engineering’ as a useful design strategy for molecular functional materials.     

Anti-Electrostatic Pi-Hole Bonding: How Covalency Conquers Coulombics

Intermolecular bonding attraction at π-bonded centers is often described as “electrostatically driven” and given quasi-classical rationalization in terms of a “pi hole” depletion region in the electrostatic potential. However, we demonstrate here that such bonding attraction also occurs between closed-shell ions of like charge, thereby yielding locally stable complexes that sharply violate classical electrostatic expectations. Standard DFT and MP2 computational methods are employed to investigate complexation of simple pi-bonded diatomic anions (BO⁻, CN⁻) with simple atomic anions (H⁻, F⁻) or with one another. Such “anti-electrostatic” anion–anion attractions are shown to lead to robust metastable binding wells (ranging up to 20–30 kcal/mol at DFT level, or still deeper at dynamically correlated MP2 level) that are shielded by broad predissociation barriers (ranging up to 1.5 Å width) from long-range ionic dissociation. Like-charge attraction at pi-centers thereby provides additional evidence for the dominance of 3-center/4-electron (3c/4e) n_D-π*_AX interactions that are fully analogous to the n_D-σ*_AH interactions of H-bonding. Using standard keyword options of natural bond orbital (NBO) analysis, we demonstrate that both n-σ* (sigma hole) and n-π* (pi hole) interactions represent simple variants of the essential resonance-type donor-acceptor (Bürgi–Dunitz-type) attraction that apparently underlies all intermolecular association phenomena of chemical interest. We further demonstrate that “deletion” of such π*-based donor-acceptor interaction obliterates the characteristic Bürgi–Dunitz signatures of pi-hole interactions, thereby establishing the unique cause/effect relationship to short-range covalency (“charge transfer”) rather than envisioned Coulombic properties of unperturbed monomers.     

Reductive Methylation of Homogeneous Primary β-Lauryl/myristyl 7/3 Polyethyleneoxy n = 3–18 Ethylamines under Phase-Transfer Catalysis Conditions

Homogeneous tertiary N,N-dimethyl-N-β-lauryl/myristyl 7/3 polyethyleneoxy n = 3–18 ethylamines, LM(EO)_nAT, are niche intermediates in the synthesis of homogeneous N-alkyl (C₁–C₁₈)-N,N-dimethyl-N-β-lauryl/myristyl 7/3 polyethyleneoxy n = 3–18 ethylammonium chlorides (unitary degree of oligomerization of ethylene oxide in the polyoxyethylene chain). This paper synthetically presents the dependence of the reductive methylation yields of homogeneous primary β-lauryl/myristyl 7/3 polyethyleneoxy n = 3–18 ethylamines, LM(EO)_nAP, on the reaction time (10–90 min), the temperature (70 °C), the molar ratio formic aldehyde /LM(EO)_nAP (1.1/1–2.5/1), the molar ratio HCOOH/LM(EO)_nAP (5/1), the degree of oligomerization of ethylene oxide in the homogeneous polyoxyethylene chain in the 3,6,9,12,18 series, and the structure of the phase-transfer catalysts. The steric effects of hydrophobic groups CH₃ and C₁₈H₃₇ grafted onto the ammonium function, and the micellar phenomena in the vicinity of their critical micellar concentration, directly proportional to the homogeneous degree of oligomerization, were highlighted. In all cases, a steady increase in reductive methylation yields was observed, with even quantitative values obtained. The high purity of the homologous series LM(EO)_nAT will allow their personalization as reference structures for the study of the evolution of basic colloidal characteristics useful in forecasting technological applications. LM(EO)_nAP were obtained either by direct amidoethylation (nucleophilic addition under basic catalysis of homogeneous lauryl/myristyl 7/3 polyethoxylated n = 3, 6, 9, 12, 18 alcohols, LM(EO)_nOH, to acrylamide monomer) or by cyanoethylation of LM(EO)_nOH under basic catalysis at 25–50 °C, in the presence of Fe²⁺ cations as oligomerization/polymerization inhibitor, followed by partial acid hydrolysis of homogeneous β-alkyl (C₁₂H₂₅/C₁₄H₂₉) 7/3 polyethyleneoxy n = 3, 6, 9, 12, 18 propionitriles, LM(EO)_nPN, to β-alkyl (C₁₂H₂₅/C₁₄H₂₉) 7/3 polyethyleneoxy n = 3, 6, 9, 12, 18 propionamides, LM(EO)_nPD, which led to LM(EO)_nAP by Hoffmann degradation. Homogeneous higher tertiary polyetheramines LM(EO)_nAT were structurally characterized.     

A small-molecule organic ferroelectric with piezoelectric voltage coefficient larger than that of lead zirconate titanate and polyvinylidene difluoride

Piezoelectric materials that generate electricity when deforming are ideal for many implantable medical sensing devices. In modern piezoelectric materials, inorganic ceramics and polymers are two important branches, represented by lead zirconate titanate (PZT) and polyvinylidene difluoride (PVDF). However, PVDF is a nondegradable plastic with poor crystallinity and a large coercive field, and PZT suffers from high sintering temperature and toxic heavy element. Here, we successfully design a metal-free small-molecule ferroelectric, 3,3-difluorocyclobutanammonium hydrochloride ((3,3-DFCBA)Cl), which has high piezoelectric voltage coefficients g₃₃ (437.2 × 10⁻³ V m N⁻¹) and g₃₁ (586.2 × 10⁻³ V m N⁻¹), a large electrostriction coefficient Q₃₃ (about 4.29 m⁴ C⁻²) and low acoustic impedance z₀ (2.25 × 10⁶ kg s⁻¹ m⁻²), significantly outperforming PZT (g₃₃ = 34 × 10⁻³ V m N⁻¹ and z₀ = 2.54 × 10⁷ kg s⁻¹ m⁻²) and PVDF (g₃₃ = 286.7 × 10⁻³ V m N⁻¹, g₃₁ = 185.9 × 10⁻³ V m N⁻¹, Q₃₃ = 1.3 m⁴ C⁻², and z₀ = 3.69 × 10⁶ kg s⁻¹ m⁻²). Such a low acoustic impedance matches that of the body (1.38–1.99 × 10⁶ kg s⁻¹ m⁻²) reasonably well, making it attractive as next-generation biocompatible piezoelectric devices for health monitoring and “disposable” invasive medical ultrasound imaging.

A small-molecule organic ferroelectric (3,3-DFCBA)Cl has high piezoelectric voltage coefficients g₃₃ (437.2 × 10⁻³ V m N⁻¹), a large electrostriction coefficient Q₃₃, and low acoustic impedance z₀, far beyond that of PZT and PVDF.     

The smallest 4f-metalla-aromatic molecule of cyclo-PrB2− with Pr–B multiple bonds

The concept of metalla-aromaticity proposed by Thorn–Hoffmann (Nouv. J. Chim. 1979, 3, 39) has been expanded to organometallic molecules of transition metals that have more than one independent electron-delocalized system. Lanthanides, with highly contracted 4f atomic orbitals, are rarely found in multiply aromatic systems. Here we report the discovery of a doubly aromatic triatomic lanthanide-boron molecule PrB₂⁻ based on a joint photoelectron spectroscopy and quantum chemical investigation. Global minimum structural searches reveal that PrB₂⁻ has a C_2v triangular structure with a paramagnetic triplet ³B₂ electronic ground state, which can be viewed as featuring a trivalent Pr(III,f²) and B₂⁴⁻. Chemical bonding analyses show that this cyclo-PrB₂⁻ species is the smallest 4f-metalla-aromatic system exhibiting σ and π double aromaticity and multiple Pr–B bonding characters. It also sheds light on the formation of the rare B₂⁴⁻ tetraanion by the high-lying 5d orbitals of the 4f-elements, completing the isoelectronic B₂⁴⁻, C₂²⁻, N₂, and O₂²⁺ series.

We report the smallest 4f-metalla-aromatic molecule of PrB₂⁻ exhibiting σ and π double aromaticity and multiple Pr–B bond characters.     

An electrically conductive metallocycle: densely packed molecular hexagons with π-stacked radicals

Electrical conduction among metallocycles has been unexplored because of the difficulty in creating electronic transport pathways. In this work, we present an electrocrystallization strategy for synthesizing an intrinsically electron-conductive metallocycle, [Ni₆(NDI-Hpz)₆(dma)₁₂(NO₃)₆]·5DMA·nH₂O (PMC-hexagon) (NDI-Hpz = N,N′-di(1H-pyrazol-4-yl)-1,4,5,8-naphthalenetetracarboxdiimide). The hexagonal metallocycle units are assembled into a densely packed ABCABC… sequence (like the fcc geometry) to construct one-dimensional (1D) helical π-stacked columns and 1D pore channels, which were maintained under the liberation of H₂O molecules. The NDI cores were partially reduced to form radicals as charge carriers, resulting in a room-temperature conductivity of (1.2–2.1) × 10⁻⁴ S cm⁻¹ (pressed pellet), which is superior to that of most NDI-based conductors including metal–organic frameworks and organic crystals. These findings open up the use of metallocycles as building blocks for fabricating conductive porous molecular materials.

Intrinsically electron-conductive metallocycle was synthesized. π-Radicals play a key role in constructing π-stacked columns among molecular hexagons and achieving high electrical conductivity over 10⁻⁴ S cm⁻¹ in polycrystalline pellet.     

Thermodynamics of Mg–Al Order-Disorder Reaction in MgAl2O4-Spinel: Constrained by Prolonged Annealing Experiments at 773–1123 K

MgAl₂O₄-spinel has wide industrial and geological applications due to its special structural and physical–chemical features. It is presumably the most important endmember of complex natural spinel solid solutions, and therefore provides a structural model for a large group of minerals with the spinel structure. There exists a well known but still inadequately understood phenomenon in the structure of MgAl₂O₄-spinel, the Mg–Al cations readily exchanging their positions in response to variations of temperature, pressure, and composition. A large number of experiments were performed to investigate the Mg–Al cation order-disorder process usually quantified by the inversion parameter x (representing either the molar fraction of Al on the tetrahedral T-sites or the molar fraction of Mg on the octahedral M-sites in the spinel structure), and some thermodynamic models were thereby constructed to describe the x-T relation. However, experimental data at some key T were absent, so that the different performance of these thermodynamic models could not be carefully evaluated. This limited the interpolation and extrapolation of the thermodynamic models. By performing some prolonged annealing experiments with some almost pure natural MgAl₂O₄-spinel plates and quantifying the x values with single-crystal X-ray diffraction technique, we obtained some critical equilibrium x values at T down to 773 K. These new x-T data, along with those relatively reliable x values at relatively high T from early studies, clearly indicate that the CS94 Model (a model constructed by Carpenter and Salje in 1994) better describes the Mg–Al cation order-disorder reaction in MgAl₂O₄-spinel for a wide range of T. On the basis of the CS94 Model, a geothermometer was established, and its form is T_-closure = 21362 × x³ − 12143 × x² + 6401 × x − 10 (T_-closure standing for the closure temperature of the Mg–Al cation exchange reaction). This geothermometer can be used to constrain the thermal history of the geological bodies containing MgAl₂O₄-spinel.     

A Study of the Effect of Sintering Conditions of Mg0.95Ni0.05Ti3 on Its Physical and Dielectric Properties

Mg_0.95Ni_0.05TiO₃ ceramics were prepared by traditional solid-state route using sintering temperatures between 1300 and 1425 °C and holding time of 2–8 h. The sintered samples were characterized for their phase composition, micro-crystalline structure, unit–cell constant, and dielectric properties. A two-phase combination region was identified over the entire compositional range. The effect of sintering conditions was analyzed for various properties. Both permittivity (ε_r) and Q factor (Q_f) were sensitive to sintering temperatures and holding times, and the optimum performance was found at 1350 °C withholding time of 4 h. The temperature coefficient of resonant frequency (τ_f) in a range from −45.2 to −52 (ppm/°C) and unit–cell constant were not sensitive to both the sintering temperature and holding time. An optimized Q factor of 192,000 (GHz) related with a permittivity (ε_r) of 17.35 and a temperature coefficient (τ_f) of −47 (ppm/°C) was realized for the specimen sintered at 1350 °C withholding time of 4 h. For applications of 5G communication device (filter, antennas, etc.), Mg_0.95Ni_0.05TiO₃ is considered to be a suitable candidate for substrate materials.     

Revealing the composition-dependent structural evolution fundamentals of bimetallic nanoparticles through an inter-particle alloying reaction

Alloy nanoparticles represent one of the most important metal materials, finding increasing applications in diverse fields of catalysis, biomedicine, and nano-optics. However, the structural evolution of bimetallic nanoparticles in their full composition spectrum has been rarely explored at the molecular and atomic levels, imparting inherent difficulties to establish a reliable structure–property relationship in practical applications. Here, through an inter-particle reaction between [Au₄₄(SR)₂₆]²⁻ and [Ag₄₄(SR)₃₀]⁴⁻ nanoparticles or nanoclusters (NCs), which possess the same number of metal atoms, but different atomic packing structures, we reveal the composition-dependent structural evolution of alloy NCs in the alloying process at the molecular and atomic levels. In particular, an inter-cluster reaction can produce three sets of Au_xAg_44−x NCs in a wide composition range, and the structure of Au_xAg_44−x NCs evolves from Ag-rich [Au_xAg_44−x(SR)₃₀]⁴⁻ (x = 1–12), to evenly mixed [Au_xAg_44−x(SR)₂₇]³⁻ (x = 19–24), and finally to Au-rich [Au_xAg_44−x(SR)₂₆]²⁻ (x = 40–43) NCs, with the increase of the Au/Ag atomic ratio in the NC composition. In addition, leveraging on real-time electrospray ionization mass spectrometry (ESI-MS), we reveal the different inter-cluster reaction mechanisms for the alloying process in the sub-3-nm regime, including partial decomposition–reconstruction and metal exchange reactions. The molecular-level inter-cluster reaction demonstrated in this study provides a fine chemistry to customize the composition and structure of bimetallic NCs in their full alloy composition spectrum, which will greatly increase the acceptance of bimetallic NCs in both basic and applied research.

An inter-particle reaction between atomically precise [Au₄₄(SR)₂₆]²⁻ (SR = thiolate) and [Ag₄₄(SR)₃₀]⁴⁻ nanoparticles reveals the composition-dependent structural evolution of alloy Au_xAg_44−x nanoparticles at the atomic level.     

Bis-Amiridines as Acetylcholinesterase and Butyrylcholinesterase Inhibitors: N-Functionalization Determines the Multitarget Anti-Alzheimer’s Activity Profile

Using two ways of functionalizing amiridine—acylation with chloroacetic acid chloride and reaction with thiophosgene—we have synthesized new homobivalent bis-amiridines joined by two different spacers—bis-N-acyl-alkylene (3) and bis-N-thiourea-alkylene (5) —as potential multifunctional agents for the treatment of Alzheimer’s disease (AD). All compounds exhibited high inhibitory activity against acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) with selectivity for BChE. These new agents displayed negligible carboxylesterase inhibition, suggesting a probable lack of untoward drug–drug interactions arising from hydrolytic biotransformation. Compounds 3 with bis-N-acyl-alkylene spacers were more potent inhibitors of both cholinesterases compared to compounds 5 and the parent amiridine. The lead compounds 3a–c exhibited an IC₅₀(AChE) = 2.9–1.4 µM, IC₅₀(BChE) = 0.13–0.067 µM, and 14–18% propidium displacement at 20 μM. Kinetic studies of compounds 3a and 5d indicated mixed-type reversible inhibition. Molecular docking revealed favorable poses in both catalytic and peripheral AChE sites. Propidium displacement from the peripheral site by the hybrids suggests their potential to hinder AChE-assisted Aβ₄₂ aggregation. Conjugates 3 had no effect on Aβ₄₂ self-aggregation, whereas compounds 5c–e (m = 4, 5, 6) showed mild (13–17%) inhibition. The greatest difference between conjugates 3 and 5 was their antioxidant activity. Bis-amiridines 3 with N-acylalkylene spacers were nearly inactive in ABTS and FRAP tests, whereas compounds 5 with thiourea in the spacers demonstrated high antioxidant activity, especially in the ABTS test (TEAC = 1.2–2.1), in agreement with their significantly lower HOMO-LUMO gap values. Calculated ADMET parameters for all conjugates predicted favorable blood–brain barrier permeability and intestinal absorption, as well as a low propensity for cardiac toxicity. Thus, it was possible to obtain amiridine derivatives whose potencies against AChE and BChE equaled (5) or exceeded (3) that of the parent compound, amiridine. Overall, based on their expanded and balanced pharmacological profiles, conjugates 5c–e appear promising for future optimization and development as multitarget anti-AD agents.