Inorganic Chemistry

Metal-organic frameworks (MOFs) are considered one of the most significant electrocatalysts for the sluggish oxygen evolution reaction (OER). Hence, a series of novel N,S-codoped Ni-based heterometallic organic framework (HMOF) ( NiM-bptz-HMOF , M = Co, Zn, and Mn; bptz = 2,5-bis((3-pyridyl)methylthio)thiadiazole) precatalysts are constructed by the heteroatom and second metal doping strategies. The effective combination of the two strategies promotes electronic conductivity and optimizes the electronic structure of the metal...

Inducing, understanding, and controlling the flexibility in metal-organic frameworks (MOFs) are of utmost interest due to the potential applications of dynamic materials in gas-related technologies. Herein, we report the synthesis of two isostructural two-dimensional (2D) interweaving zinc(II) MOFs, TMU-27 [Zn(bpipa)(bdc)] and TMU-27-NH2 [Zn(bpipa)(NH2 -bdc)], based on N , N '-bis-4-pyridyl-isophthalamide (bpipa) and 1,4-benzenedicarboxylate (bdc) or 2-amino-1,4-benzenedicarboxylate (NH2 -bdc), respectively...

Three new POM-based compounds, with formulae [Na0.63 Ag3 (Htba)2.37 (tba)0.63 (H2 O)2 (PMo12 O40 )]·4H2 O ( Ag 3 PMo ), [Ag4 (Htba)4 (H2 O)2 (PMo12 O40 )](NO3 )·H2 O ( Ag 4 PMo ), and [Ag3 (Htba)2 (tba)(PW12 O40 )0.5 ](NO3 )0.5 ·13H2 O ( Ag 3 PW ), were prepared with a 3-(4 H -1,2,4-triazol-4-yl)benzoic acid (Htba) ligand, Keggin-type anions ([PMo12 O40 ]3- /[PW12 O40 ]3- ), and a silver ion (Ag+ ). The structural features of these compounds are particularly different from the multinuclear subunits, which are [Ag3 (tba)3 ] clusters in Ag 3 PMo , [Ag4 (tba)3 ] chains in Ag 4 PMo , and [Ag3 (tba)3 ]2 clusters in Ag 3 PW , connected by multidonor atom tba ligands and Ag+ ions...

The electron transport layer (ETL) plays an important role in determining the conversion efficiency and stability of perovskite solar cells (PSCs). Here, TiO2 thin film was prepared by irradiating diisopropoxy diacetylacetone titanium precursor thin film with 172 nm vacuum ultraviolet (VUV) at a low temperature. The prepared TiO2 thin film has higher electron mobility and conductivity. As it is used as an ETL for MAPbI3 PSCs, its band structure is better matched with the perovskite, and at the same time, due to the good interface contact, more uniform perovskite crystals are formed...

Uranium-containing silica gel (UCSG) is a secondary waste generated during the advanced treatment of nuclear wastewater. In order to reduce the growing storage pressure for UCSG, from the perspective of building a borosilicate glass network, UCSG was used to replace SiO2 in the glass-cured formula to directly achieve the immobilization of UCSG. SEM-EDS results showed that uranium was uniformly distributed in the matrix, and the maximum solid solubility of UCSG (two components: silica gel and uranyl ions) in the formula was as high as 55 wt %...

A series of two-electron-oxidized cobalt porphyrin dimers have been synthesized upon controlled oxidations using halogens. Rather unexpectedly, X-ray structures of two of these complexes contain two structurally different low-spin molecules in the same asymmetric unit of their unit cells: one is the metal-centered oxidized diamagnetic entity of the type CoIII (por), while the other one is the ligand-centered oxidized paramagnetic entity of the type CoII (por•+ ). Spectroscopic, magnetic, and DFT investigations confirmed the coexistence of the two very different electronic structures both in the solid and solution phases and also revealed a ferromagnetic spin coupling between Co(II) and porphyrin π-cation radicals and a weak antiferromagnetic coupling between the π-cation radicals of two macrocycles via the bridge in the paramagnetic complex...

The discovery of novel organic-inorganic hybrid nonlinear optical (NLO) crystal materials holds great potential in advancing laser science and technology as they offer a wide range of benefits including easy synthesis, structural versatility, and high hyperpolarizability. Herein, the integration of l-tartaric acid (L-C4 H6 O6 ) and ZnSO4 gave rise to two acentric Zn-based organic-inorganic hybrid crystals, namely, Zn2 (H2 O)2 (C4 H4 O6 )2 ·3H2 O ( Zn-LT ) and Zn2 (H2 O)(C4 H4 O6 )(C4 H6 O6 )(SO4 )·4H2 O ( Zn-LTS )...

The development of stable and effective catalysts to convert toxic H2 S into high value-added sulfur is essential for production safety and environmental protection. However, the inherent defects of traditional iron- and zirconium-based catalysts, such as poor activity, high oxygen consumption, and low sulfur selectivity, limit their further developments and applications. Herein, the Fe-Zr bimetallic organic framework FeUIO-66( x ) with different cubic morphologies was synthesized via a facile solvothermal method...

The reaction of Fe2 (mes)4 with the super-bulky amidines and guanidines HL Ar*-R (LAr*-R = [(Ar*N)2 C(R)]- , Ar* = 2,6-bis(diphenylmethyl)-4- tert -butylphenyl), R = Me ( L Ar*-Me ), t Bu ( L Ar*-tBu ), Ph ( L Ar*-Ph ), Ni Pr2 ( L Ar*-iPr2N ), and Pip ( L Ar*-Pip )) gives access to the three-coordinate iron-mesityl complexes (L Ar*-R )Fe(mes) only where LAr*-R = LAr*-Me , LAr*-Ph , or LAr*-Pip . Subsequent protonolysis with the N-atom transfer reagent Hdbabh (Hdbabh = 2,3:5,6-dibenzo-7-azabicyclo[2.2.1]hepta-2,5-diene) is limited in success, providing in one instance a few crystals of four-coordinate (L Ar*-Me )Fe(dbabh)(Hdbabh) , while three-coordinate (L Ar*-Pip )Fe(dbabh) is synthesized reproducibly...

This article presents the utilization of a cylindrical double-tube shock loading device in conjunction with amorphous red phosphorus as the precursor to investigate the complete phase transformation of red phosphorus into black phosphorus under the influence of shockwaves. Multiple experiments were conducted by varying the shock pressure and temperature parameters. The characterization of the recovered samples involved analysis of the phase composition and microstructure. The obtained experimental results demonstrate that within the cylindrical double-tube shock loading setup, a pressure of 9 GPa and a temperature of 800 K are optimal for achieving the complete phase transition of amorphous red phosphorus into orthorhombic black phosphorus...

SnTe is an environmentally friendly medium-temperature thermoelectric material, but its inherent low power factor (PF) and high lattice thermal conductivity severely limit its application. In this study, based on the fact that Mn doping can induce band convergence, the high-pressure and high-temperature (HPHT) synthesis method was used to optimize the sample preparation and shorten the synthesis cycle to 30 min. The results show that the Sn0.93 Mn0.10 Te sample achieves the maximum PF value of 34.00 μW cm-1 K-2 at 775 K and PFave value of 21...

Phosphor-converted white-light-emitting diodes (WLEDs) with superhigh color rendering index (CRI) are the ongoing pursuit of next-generation solid-state lighting. One of the most important challenges is the limited improvement in CRI on account of the absence of a cyan component in the typical commercial combination. Here, a bright broad-band cyan-green-emitting phosphor with cubic garnet structure, SrLu2 Al3 ScSiO12 :Ce3+ (SLASSO:Ce3+ ), was successfully reported, which can compensate for the absence of cyan cavity in the 480-520 nm blue-green emission region...

This work reports the synthesis of a dual functional 2D framework, {[Zn2 (4-tpom)2 (oxdz)2 ]·4H2 O}n ( 1 ), at room temperature, where a bent dicarboxylate, oxdz2- (4,4'-(1,3,4-oxadiazole-2,5-diyl)dibenzoate), and a neutral flexible N-donor linker, 4-tpom (tetrakis(4-pyridyloxymethylene)methane), are utilized. Its single-crystal X-ray analysis indicated a 2-fold interpenetrated 2D framework having tetracoordinated Zn(II) centers and dangling pyridyl groups. Its further characterization was carried out with elemental microanalysis, FTIR spectroscopy, TG analysis, and powder X-ray diffraction...

Rare earth-based halide double perovskites are regarded as an emerging class of X-ray scintillation materials. However, the majority of related scintillator applications are still focused on single crystal and powder systems; the application of nanocrystal (NC) scintillators is rarely reported. Here, we present the synthesis of high-purity Cs2 NaTbCl6 NCs by an improved hot-injection method. Interestingly, hollow Cs2 NaTbCl6 NCs are observed, the monitoring of the growth process indicates that micrometer-sized NaCl is the initial product, and then the NaCl would convert into Cs2 NaTbCl6 NCs through the diffusion of Cs+ and Tb3+ into NaCl lattice, and the faster outward diffusion of Na+ results in the formation of hollow NCs...

The unusually high oxidation state + IV of cobalt is stabilized by ligands based on [B11 H11 ]4- in dark blue colored Cs4 [Co(B11 H10.11 (OH)0.75 )2 ]·4.56H2 O, K4 [Co(B11 H9.19 (OH)1.81 )2 ]·2H2 O, Cs8 [Co{(B11 H6 )2 (O)(O2 BOH)4 }]2 ·4H2 O and K4 [Co{(B11 H6 )2 (O2 BOH)5 }]·7H2 O. These compounds were obtained by reacting Co2+ salts with [B11 H14 ]- under alkaline conditions. In the absence of oxygen, Co(+III) compounds such as the light brownish K4 [Co(B11 H11 )(CN)3 ]·KCl·2...

[Pt(NCN)MeCN]+ (NCN = 1,3-di(2-pyridyl)benzene, MeCN = acetonitrile) forms oligomers, such as dimers and trimers, in solutions due to metallophilic interactions. The emission and absorption spectra in the visible region are considerably changed by the concentrations of the solutions because the excitation energy of the oligomers is dependent on the degree of oligomerization. In this study, excited-state dynamics of [Pt(NCN)MeCN]+ in acetonitrile were investigated by time-resolved emission spectroscopy in time regions from microseconds to nanoseconds at various concentrations...

The significant threat posed by the high toxicity of heavy metals and antibiotics in water pollutants has prompted a growing emphasis on the development of highly efficient removal methods for these pollutants. In this paper, flexible electrospinning polyacrylonitrile (PAN) nanofiber-supported CdBi2 S4 was synthesized via a hydrothermal method, followed by amination treatment with diethylenetriamine (DETA). The as-prepared CdBi2 S4 /NH2 -PAN nanofiber, enriched with sulfur vacancies, demonstrated outstanding visible-light trapping ability and a suitable band gap, leading to efficient separation and transport of photogenerated carriers, ultimately resulting in exceptional photocatalytic capability...

In the present study, we have investigated the stability of different Ba-Si clathrates with pressure and temperature using DFT calculations and studied the stability of type I Ba8 Si46 and type IX Ba24 Si100 clathrates using high pressure─high temperature synthesis technique, calorimetry, and diffraction experiments. When increasing pressure, the type I Ba8 Si46 clathrate and BaSi6 become more stable. In good qualitative agreement with experiments, the type IX Ba24 Si100 clathrate becomes stable at a pressure of 1-2 GPa thanks to the pressure and thermal effect of both electronic and vibrational contributions...

Transparent and brown La2 O3 -MoO3 binary glasses were prepared in bulk form using a levitation technique. The glass-forming range was limited, with the primary composition being approximately 25 mol % La2 O3 . The 25La2 O3 -75MoO3 glass exhibited a clear crystallization at 546 °C, while determining its glass transition temperature was difficult. Notably, despite its amorphous nature, the glass possessed a density and packing density comparable to those of crystalline La2 Mo3 O12 . X-ray absorption fine structure and Raman scattering analyses revealed that the glass structure closely resembles La2 Mo3 O12 due to the presence of isolated MoO4 2- units, whereas disordered atomic arrangement around La atoms was confirmed...

Introduction of oxygen into aromatic C-H bonds is intriguing from both fundamental and practical perspectives. Although the 3d metal-catalyzed hydroxylation of arenes by H2 O2 has been developed by several prominent researchers, a definitive mechanism for these crucial transformations remains elusive. Herein, density functional theory calculations were used to shed light on the mechanism of the established hydroxylation reaction of benzene with H2 O2 , catalyzed by [NiII (tepa)]2+ (tepa = tris[2-(pyridin-2-yl)ethyl]amine)...