inorganic chemistry

Two novel MoO4 2- -templated luminescent silver alkynyl nanoclusters with 20-nuclearity ([(MoO4 2- )@Ag20 (C≡C t Bu)8 (Ph2 PO2 )7 (tfa)2 ]·(tfa- ) ( 1 )) and 18-nuclearity ([(MoO4 2- )@Ag18 (C≡C t Bu)8 (Ph2 PO2 )7 ]·(OH) ( 2 )) (tfa = trifluoroacetate) were synthesized with the green light maximum emissions at 507 and 516 nm, respectively. The nanoclusters were investigated and characterized by single-crystal X-ray crystallography, electrospray ionization mass spectrum (ESI-MS), X-ray photoelectron spectroscopy, thermogravimetry (TG), photoluminescence (PL), ultraviolet-visible (UV-vis) spectroscopy, and density functional theory calculations (DFT)...

The metal borides, Hf2 MOs5 B2 (M = Mn, Fe, Co), which are the first Os-rich quaternary variants of the prolific Ti3 Co5 B2 structure type, were investigated computationally and experimentally. In their crystal structures, osmium builds a network of prisms, in which the other elements are located. The magnetic M elements are found in face-connected Os8 square prisms leading to M-chains with intra- and interchain distances of about 3.0 and 6.5 Å, respectively. Density functional theory (DFT) showed that magnetic ordering is hugely favored for M = Mn and Fe but only slightly favored for M = Co...

The reactivity of six MnIV -oxo complexes in C-H bond oxidation has been examined using a combination of kinetic experiments and computational methods. Variable-temperature studies of the oxidation of 9,10-dihydroanthracene (DHA) and ethylbenzene by these MnIV -oxo complexes yielded activation parameters suitable for evaluating electronic structure computations. Complementary kinetic experiments of the oxidation of deuterated DHA provided evidence for hydrogen-atom tunneling in C-H bond oxidation for all MnIV -oxo complexes...

Noncentrosymmetric chalcogenides are promising candidates for infrared nonlinear-optical (NLO) crystals, and exploring high-performance ones is a hot topic and challengeable. Herein, the combination of AgQ4 , InQ4 , and SiQ4 (Q = S, Se) units with different S/Se ratios resulted in the discovery of the tetrahedral chalcogenides Ag2 In2 SiS4 Se2 ( 1 ) and Ag2 In2 SiS5 Se ( 2 ). They both crystallize in the monoclinic Cc space group with different local structures. Co-occupied S/Se sites only exist in 2 , and the arrangement of [In2 SiQ3 ] six-membered rings builds different helical chains and 3D [(In2 SiQ6 )2- ] n polyanionic frameworks in 1 and 2 ...

Nanomaterials have attracted great interest in the field of photocatalytic degradation due to their larger specific surface area and efficient charge/mass transfer ability, which are beneficial for enhancing photocatalytic activity. However, the bandgap of photocatalysts would increase with the size reduction, weakening the photoabsorption ability. Thus the relationship between the size of catalysts and photoactivity should be balanced to achieve optimal photocatalytic performance. Herein, ultra-small CuWO4 nanoparticles ( ca...

This study investigates the influence of ligand charge on transition energies in a series of CuN2 S2 complexes based on dithiocarbazate Schiff base ligands using Cu K-edge X-ray absorption spectroscopy (XAS) and Kβ valence-to-core (VtC) X-ray emission spectroscopy (XES). By comparing the formally Cu(II) complexes [CuII(HL1)] (HL12- = dimethyl pentane-2,4-diylidenebis[carbonodithiohydrazonate]) and [CuII(HL2)] (HL22- = dibenzyl pentane-2,4-diylidenebis[carbonodithiohydrazonate]) and the formally Cu(III) complex [CuIII(L2)], distinct changes in transition energies are observed, primarily attributed to the metal oxidation state...

The synthesis of copper (Cu) nanoclusters (NCs) has experienced significant advancements in recent years. Despite the exploration of metal NCs dating back almost two decades, challenges specific to Cu NC synthesis arise from the variable oxidation states and heightened reactivity of intermediate Cu complexes, distinguishing it from its analogous counterparts. In this study, we present a comprehensive overview of this newly evolving research domain, focusing on the synthetic aspects. We delve into various factors influencing the synthesis of Cu NCs, with specific emphasis on the role of reducing agents...

Capillary electrophoresis with capacitively coupled contactless conductivity detection (CE-C4 D) has the advantages of high throughput (simultaneous detection of multiple ions), high separation efficiency (higher than 105 theoretical plates) and rapid analysis capability (less than 5 min for common inorganic ions). A compact CE-C4 D system is ideal for water quality control and on-site analysis. It is suitable not only for common cations ( e.g. Na+ , K+ , Li+ , NH4 + , Ca2+ , etc .) and anions ( e.g. Cl- , SO4 2- , BrO3 - , etc ...

Homogeneous transition metal catalysis is a constantly developing field in chemical sciences. A growing interest in this area is photoswitchable catalysis, which pursues in situ modulation of catalyst activity through noninvasive light irradiation. Phosphorus ligands are excellent targets to accomplish this goal by introducing photoswitchable moieties; however, only a limited number of examples have been reported so far. In this work, we have developed a series of palladium complexes capable of catalyzing the Stille coupling reaction that contain photoisomerizable phosphine ligands based on dithienylethene switches...

Rare-earth tris-diketonato [RE(dike)3 pyterpy] metalloligands can be prepared reacting at room temperature [RE(dike)3 dme] (dme = 1,2-dimethoxyethane; dike = tta with Htta = 2-thenoyltrifluoroacetone and RE = La, 1 ; Y, 2 ; Eu, 3 ; Dy, 4 ; or dike = hfac with Hhfac hexafluoroacetylacetone, and RE = Eu, 5 ; Tb, 6 ; Yb 7 ) with 4'-(4‴-pyridil)-2,2':6',2″-terpyridine (pyterpy). The molecular structures of 1 , 5 , 6 , and 7 have been studied through single-crystal X-ray diffraction showing mononuclear neutral complexes with the rare-earth ion in coordination number nine and with a muffin-like coordination geometry...

Thermodynamics and kinetics of hydroxide ion binding to iron tetraphenylporphyrin (TPPFe) at different redox states is investigated by electrochemistry and UV-vis spectroscopy. The reduction of initial TPPFe(III) drastically decreases the binding affinity of hydroxide ions. An activation-driving force correlation is revealed showing that the strongest the binding affinity, the largest the association rate constant and vice versa. Comparison with chloride ions shows that hydroxide ions are stronger ligands for iron tetraphenylporphyrin...

Two monometallic and three bimetallic ruthenium acetonitrile (RuMeCN) complexes are presented and fully characterized. All of them are built from the same skeleton [FTRu(bpy)(MeCN)]2+ , in which FT is a fluorenyl-substituted terpyridine ligand and bpy is the 2,2'-bipyridine. The crystal structure of [FTRu(bpy)(MeCN)](PF6 )2 is presented. A careful spectroscopic analysis allows establishing that these 5 RuMeCN complexes can be identified as the product of the photoreaction of 5 related RuNO complexes, investigated as efficient nitric oxide (NO) donors...

Production of thermoelectric materials from solution-processed particles involves the synthesis of particles, their purification and densification into pelletized material. Chemical changes that occur during each one of these steps render them performance determining. Particularly the purification steps, bypassed in conventional solid-state synthesis, are the cause for large discrepancies among similar solution-processed materials. In present work, the investigation focuses on a water-based surfactant free solution synthesis of SnSe, a highly relevant thermoelectric material...

Among numerous biologically important metal cations, strontium (Sr2+ ) has received much attention in bone tissue regeneration because of its osteoinductive properties combined with its ability to inhibit osteoclast activity. In this study, strontium-doped hydroxyapatite (Sr-HAp) nanorods with varying molar ratios of Ca : Sr (10 : 0, 9 : 1, 5 : 5, 3 : 7 and 0 : 10) were synthesized using the chemical precipitation technique...

Transition and rare earth metals serve as indispensable raw materials across a broad spectrum of technological applications. However, their utilization is frequently linked to substantial waste production. Consequently, the recycling and recovery of these metals from end-of-life products or metal-contaminated aqueous environments hold significant importance within the framework of a circular economy. In our investigation, we employed synthetic mesoporous silica monoliths, synthesized via the sol-gel method and functionalized with chelating groups, for the efficient recovery of metal ions from aqueous matrices...

The spinels ZnAl1.99- x Ho x Cr0.01 O4 (with x = 0 and 0.001) were synthesized using a solid-state method, and various techniques were employed for their characterization. X-ray diffraction (XRD) analysis confirmed a cubic spinel structure with the Fd 3̄ m space group for both spinels. The morphology and homogeneity of the chemical composition were determined using scanning electron microscopy (SEM) and energy dispersive X-ray analysis. Raman and infrared vibrational spectroscopy techniques were also employed for analysis...

We describe the mononuclear anionic cyanido-pentafluorophenyl complexes, (NBu4 )[Pt(C^N)(C6 F5 )(CN)] [C^N = 7,8-benzoquinolate (bzq) 1, 2-(2,4-difluorophenyl)pyridinate (dfppy) 2] and the heteropolynuclear derivatives [{Pt(C^N)(C6 F5 )(CN)}Tl] (C^N = bzq 3, dfppy 4). These complexes were synthesized via a two-step modular synthesis by reaction of the corresponding potassium salts K[Pt(C^N)(C6 F5 )(CN)], prepared in situ from [Pt(C^N)(C6 F5 )(DMSO)] and KCN in acetone/H2 O, with TlPF6 . The structures of {[Pt(bzq)(C6 F5 )(CN)Tl]·THF} n (3·THF) n and [{Pt(dfppy)(C6 F5 )(CN)}Tl]4 ·dioxane [4]4·dioxane, determined by X-ray crystallography, confirm the presence of Pt(II)-Tl(I) bonds [2...

This study investigated the effect of plasma treatment on reused water and evaluated the interactions of the plasma-treated water (PTW) with plants or microbes to determine the optimal PTW for reuse. The repeated treatment gradually accumulated nitrate (NO3 - ) in the PTW and lowered its pH; afterward, it led to the sprouted soybeans accumulating other inorganic ions in the PTW. The biomass of soybean sprouts was enhanced by the accumulated NO3 - but decreased due to the pH effect. Meanwhile, the acidic pH reduced the microbial counts, but they increased after sprinkling the PTW over the sprouts...

Layered carbides are fascinating compounds due to their enormous structural and chemical diversity, as well as their potential to possess useful and tunable functional properties. Their preparation, however, is challenging and forces synthesis scientists to develop creative and innovative strategies to access high-quality materials. One unique compound among carbides is Mo2 Ga2 C. Its structure is related to the large and steadily growing family of 211 MAX phases that crystallize in a hexagonal structure (space group P 63 / mmc ) with alternating layers of edge-sharing M 6 X octahedra and layers of the A -element...

The "cyan gap" is the bottleneck problem in violet-driven full-spectrum white-light-emitting diodes (wLEDs) in healthy lighting. Accordingly, we develop a novel broadband-blue-cyan emission Na3 KMg7 (PO4 )6- x (BO3 ) x :Eu2+ (NKMPB:Eu2+ ) phosphor via crystal-site engineering. This phosphor is derived from the Na3 KMg7 (PO4 )6 :Eu2+ phosphor, which shows desired abundant cyan emissive components. A comparative study is conducted to reveal the microstructure-property relationship and the key influential factors to its spectrum distribution...