Inorganic Chemistry

Herein, two Laves intermetallic series, ZrCo1.75 M 0.25 and NbCo1.75 M 0.25 ( M = Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, and Pt), were synthesized, and their hydrogen evolution reaction (HER) activities were examined to reveal the influence of d electrons to the corresponding HER activities. Owing to the different electronegativity between Zr and Nb (χZr = 1.33; χNb = 1.60), Co and/or M elements receive more electrons in ZrCo1.75 M 0.25 than that of the Nb one. This leads to the overall weak H adsorption energy (Δ G Had ) of ZrCo1...

Light-emitting electrochemical cells (LECs) promise low-cost, large-area luminescence applications with air-stabilized electrodes and a versatile fabrication that enables the use of solution processes. Nevertheless, the commercialization of LECs is still encountering many obstacles, such as low electroluminescence (EL) efficiencies of the ionic materials. In this paper, we propose five blue to yellow ionic Ir complexes possessing 4-fluoro-4'-pyrazolyl-(1,1'-biphenyl)-2-carbonitrile ( ppfn ) as a novel cyclometalating ligand and use them in LECs...

Zirconium/hafnium fluorides have recently been recognized as potential nonlinear optical (NLO) materials with short ultraviolet (UV) cutoff edges, which is significant in laser science and industry. The synthesis of noncentrosymmetric (NCS) materials based on centrosymmetric (CS) compounds by an isovalent cation substitution-oriented design is an emerging strategy in the NLO territory. Here, two isostructural and novel fluorides, CaBaMF8 (M = Zr ( 1 ), Hf ( 2 )), have been synthesized through the combination of alkaline earth metals, zirconium/hafnium, and fluorine elements...

A monoanionic phosphoramide ligand is introduced, which forms a series of lanthanum complexes with the ligand in both anionic and neutral forms. Stoichiometric control alone provides monometallic complexes with either two or three phosphoramide ligands. Alternatively, a combination of anionic and neutral proteo ligands featuring intramolecular hydrogen bonding can be obtained. The anionic form of the ligand binds lanthanum as a bi- or monodentate ligand, depending on the steric demand at the metal center, while the protonated ligand binds exclusively through the phosphoramide oxygen donor...

Adsorption separation of the Xe/Kr mixture remains a tough issue since Xe and Kr have an inert nature and similar sizes. Here we present a chlorinated metal-organic framework (MOF) [JXNU-19(Cl)] and its nonchlorinated analogue (JXNU-19) for Xe/Kr separation. The two isostructural MOFs constructed from the heptanuclear cobalt-hydroxyl clusters bridged by organic ligands are three-dimensional structures. Detailed contrast of the Xe/Kr adsorption separation properties of the MOF shows that significantly enhanced Xe uptakes and Xe/Kr adsorption selectivity (17...

Two new congruently melting Pb-containing halogen silicates, Pb3 [O10 Pb20 ](SiO4 )4 X10 (X = Cl, Br), have been synthesized using a high-temperature solution method. Their crystal structures were determined by single-crystal X-ray diffraction, and both compounds crystallize in the orthorhombic space group Cmca . In both structures, the mirror-symmetric bilayer composed of Pb-O polyhedra is observed for the first time in Pb-containing silicates and belongs to α-PbO derivatives and is related to the Aurivillius phase...

A benchmark set for the computation of 207 Pb nuclear magnetic resonance (NMR) chemical shifts is presented. The PbS50 set includes conformer ensembles of 50 lead-containing molecular compounds and their experimentally measured 207 Pb NMR chemical shifts. Various bonding motifs at the Pb center with up to seven bonding partners are included. Six different solvents were used in the measurements. The respective shifts lie in the range between +10745 and -5030 ppm. Several calculation settings are assessed by evaluating computed 207 Pb NMR shifts for the use with different density functional approximations (DFAs), relativistic approaches, treatment of the conformational space, and levels for geometry optimization...

The discovery of ferrocene in 1951 was a significant landmark in the field of organometallic chemistry, and since then, numerous sandwich- or half-sandwich metallic complexes have been reported. However, silver stands as an intriguing exception in this regard, and knowledge of its bonding situation has remained undisclosed. Herein, unprecedented 12-vertex metallacarboranes of Ag(I) ( 2a and 2b ) were synthesized through the reaction of sodium hexamethyldisilazide (NaHMDS) with the mixture of nido -C2 B9 carborane anion-supported N -heterocyclic carbene precursors ( 1a and 1b ) and [Ag(PPh3 )Cl]4 ...

Exploring highly effective bifunctional electrocatalysts with surface structural advantages and synergistic optimization effects among multimetals is greatly important for overall water splitting. Herein, we successfully synthesized Pt-loaded NiFe-metal-organic framework nanosheet arrays grown on nickel foam (Pt-NiFe-MOF/NF) via a facile hydrothermal-electrodeposition process. Benefiting from large exposed specific surface, optimal electrical conductivity and efficient metal-support interaction endow Pt-NiFe-MOF/NF with highly catalytic performance, exhibiting small overpotential of 261 mV toward oxygen evolution reaction and 125 mV toward hydrogen evolution reaction at a current density of 100 mA cm-2 in alkaline medium...

The construction of photocatalysts with a surface plasmon resonance effect (SPR) has been demonstrated as a highly effective strategy for enhancing photocatalytic efficiency. In this paper, we synthesized a catalyst with bismuth metal loaded on ZnCdS nanospheres for an efficient photocatalytic nitrogen reduction reaction (PNRR). The SPR effect induced by Bi nanoparticles under light excitation significantly promoted the ammonia production efficiency of the photocatalyst. Under air ambient conditions with lactic acid as the sacrificial agent, the photocatalytic NH4 + yield of 3% Bi@ZnCdS was 58...

The first chiral and luminescent cyclic trinuclear gold(I) complex, [{AuCH(PPh2 Me)(Ph2 P)}3 ]3+ , has been isolated with metalated phosphorus ylides (PY). This complex was initially obtained through the reaction of either mononuclear [C6 F5 SAuCH(PPh2 Me)(Ph2 P)]OTf or dinuclear [C6 F5 S{AuCH(PPh2 Me)(Ph2 P)}2 ](OTf)2 thiolate-gold-phosphane complexes in the presence of NaH, followed by the abstraction of the thiopyridine moiety employing either AgOTf or [Cu(CH3 CN)4 ]PF6 . Our quest for a more efficient synthesis route led to the development of a streamlined one-pot synthesis method, employing Ag(acac) as both a halogen abstractor and a base, offering a quicker and more direct path to this intriguing trimer...

Osteosarcoma cancers are becoming more common in children and young adults, and existing treatments have low efficacy and a very high mortality rate, making it pressing to search for new chemotherapies with high efficacy and high selectivity index. Copper complexes have shown promise in the treatment of osteosarcoma. Here, we report the synthesis, characterization, and anticancer activity of [Cu(N-N-Fur)(NO3 )(H2 O)] complex where N-N-Fur is (E)- N '-(2-hydroxy-3-methoxybenzylidene)furan-2-carbohydrazide. The [Cu(N-N-Fur)(NO3 )(H2 O)] complex was characterized via X-ray diffraction and electron spin resonance (ESR), displaying a copper center in a nearly squared pyramid environment with the nitrate ligand acting as a fifth ligand in the coordination sphere...

The development of high-efficiency heterojunction photocatalysts has been recognized as an effective approach to facilitate photocatalytic CO2 reduction. In this research, we successfully synthesized a novel multiflower-like ReS2 /NiAl-LDH heterojunction through a hydrothermal method. Remarkably, when exposed to visible-light irradiation, 2-ReS2 /NiAl-LDH demonstrated an exceptional CO production rate of 272.26 μmol·g-1 ·h-1 , which was 4.0 and 10.8 times higher than that of pristine NiAl-LDH and ReS2 ...

We report a directed two-step synthesis toward pentanuclear Kuratowski complexes. First, six 5,6-dimethylbenzo[1,2,3]triazole ligands (Me2 btaH) are coordinated to a single Ru(II) ion, providing a topologically ideal template for the addition of further metal ions. The synthesis and crystal structures of [RuCu4 X4 (Me2 bta)6 ] [X = acetylacetonate (acac) and tris(3,5-dimethyl-1-pyrazolyl)borate (Tp*)] are described. Both represent new members of the family of so-called Kuratowski (K3,3 ) complexes. The coordination units feature triazolato-bridged metal-centered {MM4 } tetrahedra, which are known for frustrated magnetic interactions in both complexes and metal-organic frameworks...

Single-wall nanotubes of isostructural AsPS4- x Se x ( x = 0, 1) are grown from solid-state reaction of stoichiometric amounts of the elements. The structure of AsPS4 was determined using single-crystal X-ray diffraction and refined in space group <mml:math xmlns:mml="https://www.w3.org/1998/Math/MathML"><mml:mi>P</mml:mi><mml:mover><mml:mn>1</mml:mn><mml:mo>¯</mml:mo></mml:mover></mml:math>. The infinite, single-walled AsPS4 nanotubes have an outer diameter of ≈1...

The recent discovery of superconductivity in the Ruddlesden-Popper bilayer nickelate, specifically La3 Ni2 O7 , has generated significant interest in the exploration of high-temperature superconductivity within this material family. In this study, we present the crystallographic and electrical resistivity properties of two distinct Ruddlesden-Popper nickelates: the bilayer La3 Ni2 O7 (referred to as 2222-phase) and a previously uncharacterized phase, La3 Ni2 O7 (1313-phase). The 2222-phase is characterized by a pseudo F -centered orthorhombic lattice, featuring bilayer perovskite [LaNiO3 ] layers interspaced by rock salt [LaO] layers, forming a repeated ...

The triple bond in N2 is significantly stronger than the double bond in O2 , meaning that synthesizing nitrogen-rich nitrides typically requires activated nitrogen precursors, such as ammonia, plasma-cracked atomic nitrogen, or high-pressure N2 . Here, we report a synthesis of nitrogen-rich nitrides under ambient pressure and atmosphere. Using Na2 MoO4 and dicyandiamide precursors, we synthesized nitrogen-rich γ-Mo2 N3 in an alumina crucible under an ambient atmosphere, heated in a box furnace between 500 and 600 °C...

Various pathways for the synthesis of beryllium triflate were investigated. The reaction of triflic acid or trimethylsilyl triflate with beryllium metal in liquid ammonia led to the formation of mono-, di-, and tetra-nuclear beryllium ammine complexes. Utilization of SMe2 as a solvent gave homoleptic Be(OTf)2 . Various beryllium triflate complexes with N- and O-donor ligands as well as the complex anions [Be(OTf)4 ]2- and [Be2 (OTf)6 ]2- were synthesized to evaluate the reactivity and solution properties of beryllium triflate...

The concept of high-entropy oxides has triggered extensive research of this novel class of materials because their numerous functional properties are usually not mere linear combinations of those of the components. Here, we introduce the new series of compositionally complex honeycomb-layered magnets Na3- x Li x T2 SbO6 (T = Cu1/3 Ni1/3 Co1/3 ). An unusual feature of the system is its nonmonotonous dependences of the monoclinic lattice parameters b and β on x . Rietveld refinement of the crystal structures of the Na and Li end members reveals apparent Sb-T site inversion in the former and considerable Li-Cu site inversion in the latter...

Reported are the syntheses, structural characterizations, and luminescence properties of three novel [UO2 Cl4 ]2- bearing compounds containing substituted 1,1'-dialkyl-4,4'-bipyridinum dications (i.e., viologens). These compounds undergo photoinduced luminescence quenching upon exposure to UV radiation. This reactivity is concurrent with two phenomena: radicalization of the uranyl tetrachloride anion and photoelectron transfer to the viologen which constitutes the formal transfer of one electron from [UO2 Cl4 ]2- to the viologen species...