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 ...

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...

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...

The structure and Li conductivity has been investigated in the Li1+ x Ti2- x In x (PO4 )3 (0 ≤ x ≤ 2) series prepared by the ceramic route at 900 °C. The XRD patterns of 0 ≤ x ≤ 0.2 samples show the presence of rhombohedral (S.G. R 3̅ c ); those of 0.2 ≤ x ≤ 1 samples display both rhombohedral and orthorhombic (S.G. Pbca ), and 1 ≤ x ≤ 2 samples exhibit only monoclinic (S.G. P 21 / n ) phases. At intermediate compositions, the secondary LiTiPO5 phase was detected...

Heteroatom doping and heterostructure construction are the key methods to improve the performance of electrocatalysts. However, developing such catalysts remains a challenging task. Herein, we designed two comparable polymers, phytic acid/thiourea polymer (PATP) and phytic acid/urea polymer (PAUP), as precursors, which contain C, N, S/O, and P by microwave heating. To pinpoint how the introduction of sulfur would affect the electronic structure and catalytic activity, these two polymers were physically blended with CoCo-Prussian blue analogue (CoCo-PBA) and further calcination, respectively...

In the quest for proficient electrocatalysts for ammonia's electrocatalytic nitrogen reduction, cobalt oxides, endowed with a rich d-electron reservoir, have emerged as frontrunners. Despite the previously evidenced prowess of CoO in this realm, its ammonia yield witnesses a pronounced decline as the reaction unfolds, a phenomenon linked to the electron attrition from its Co2+ active sites during electrocatalytic nitrogen reduction reaction (ENRR). To counteract this vulnerability, we harnessed electron-laden phosphorus (P) elements as dopants, aiming to recalibrate the electronic equilibrium of the pivotal Co active site, thereby bolstering both its catalytic performance and stability...

Herein, three In(III)-based metal-organic frameworks (In-MOFs) with different degrees of interpenetration (DOI), namely In-MOF-1, In-MOF-2, and In-MOF-3, constructed by In3+ and Y-shaped ligands 4,4',4″-s-triazine-2,4,6-triyltribenzoate (H3 TATB), are successfully synthesized through the ionothermal/solvothermal method. Subsequently, three novel In-MOFs, including noninterpenetration polycatenation, 2-fold interpenetrated, and 4-fold interpenetrated structure, are employed as the platform for systematically investigating the separation efficiency of CO2 /N2 , CO2 /CH4 , and CO2 /CH4 /N2 mixture gas system...

We designed [VO(bdhb)] ( 1 ') as a new electronic qubit containing an oxovanadium(IV) ion ( S = 1/2) embraced by a single bis(β-diketonato) ligand [H2 bdhb = 1,3-bis(3,5-dioxo-1-hexyl)benzene]. The synthesis afforded three different crystal phases, all of which unexpectedly contain dimers with formula [(VO)2 (bdhb)2 ] ( 1 ). A trigonal form ( 1 h ) with a honeycomb structure and 46% of solvent-accessible voids quantitatively transforms over time into a monoclinic solvatomorph 1 m and minor amounts of a triclinic solventless phase ( 1 a )...

Hybrid ferroelastic crystals have emerged as a hot research topic in recent years owing to their prospective applications in piezoelectric sensors, mechanical switches, and optoelectronic devices. Nevertheless, most of the documented materials exhibit one-step or two-step ferroelastic phase transition(s), and those with multistep ferroelastic transitions are extremely scarce. We present a new hexagonal molecular perovskite based on a fluoro-substituted flexible cyclic ammonium cation, (1-fluoromethyl-1-methylpyrrolidine)[CdCl3 ] ( 1 ), undergoing unusual three-step ferroelastic phase transitions from hexagonal paraelastic phase to orthorhombic, monoclinic, and triclinic ferroelastic phases at 388, 376, and 311 K, respectively, with Aizu notation of 6/ mmm F mmm , mmm F2/ m , and 2/ m F-1, featuring spontaneous strain of 0...

Metallodrug-based photodynamic therapy (PDT) agents have demonstrated significant superiority against cancers, while their different chirality-induced biological activities remain largely unexplored. In this work, we successfully developed a pair of enantiopure mononuclear Ir(III)-based TLD-1433 analogues, Δ-Ir-3T and Λ - Ir-3T , and their enantiomer-dependent anticancer behaviors were investigated. Photophysical measurements revealed that they display high photostability and chemical stability, strong absorption at 400 nm with high molar extinction coefficients (ε = 5...

Advancing the progress of sustainable and green energy technologies requires the improvement of valid electrocatalysts for the hydrogen evolution reaction (HER). Reconfiguring charge distribution through heteroatom doping-induced vacancy serves as an effective approach to implement high performance for HER catalysts. Here, we successfully fabricated Fe-doped CuS (FeCuS) with the sublayer sulfur vacancy to judge its HER performance and dissect the activity origins. Density functional theory calculation further elucidates that the primary factor contributing to the heightened HER activity is that the sublayer sulfur vacancies awaken the charge redistribution...

Dysregulated cathepsin activity is linked to various human diseases including metabolic disorders, autoimmune conditions, and cancer. Given the overexpression of cathepsin in the tumor microenvironment, cathepsin inhibitors are promising pharmacological agents and drug delivery vehicles for cancer treatment. In this study, we describe the synthesis and photochemical and biological assessment of a dual-action agent based on ruthenium that is conjugated with a cathepsin inhibitor, designed for both photodynamic therapy (PDT) and photochemotherapy (PCT)...

[Ln·DOTA]- complexes and systems derived therefrom are commonly used in MRI and optical bioimaging. These lanthanide(III) complexes are chiral, and, in solution, they are present in four forms, with two sets of enantiomers, with the ligand donors arranged in either a square antiprismatic, SAP, or twisted square antiprismatic geometry, TSAP. This complicated speciation is found in laboratory samples. To investigate speciation in biological media, when Ln·DOTA-like complexes interact with chiral biomolecules, six Eu·DOTA-monoamide complexes were prepared and investigated by using 1D and 2D 1 H NMR...