Inorganic Chemistry最新文献

Diamagnetic metal sulfonates have been widely reported, while paramagnetic species are very rare, especially those that exhibit interesting magnetic and/or proton conduction properties. Herein, we report the synthesis, structure, magnetic, and proton-conducting properties of a hydrogen-bonded cobalt(II) organosulfonate complex. The coordination self-assembly of Co^II salts and 8-quinolinesulfonic acid ligands affords a mononuclear Co^II sulfonate featuring both coordinated and noncoordinated sulfonic acid O atoms and axial coordinated water molecules. Notably, the Co^II units are further connected by short S-O···H-O hydrogen-bonding interactions between SO₃^- and coordinated H₂O, leading to a three-dimensional (3D) hydrogen-bonded network. This hydrogen-bonded sulfonate exhibits superior thermal stability, as proved by variable-temperature single-crystal and powder X-ray diffraction and thermogravimetric analysis (TGA) analysis. Variable-temperature and variable humidity ac impedance spectroscopy indicated this cobalt sulfonate is a good superionic proton conductor with the highest measured conductivity of 1.5 × 10^-3 S cm^-1 at 90 °C under 97% relative humility, originating from 1D zigzag hydrogen-bonded chains. In addition, field-induced slow magnetic relaxation was observed via dynamic ac magnetic susceptibility measurements. These results show not only the first proton-conducting Co(II) single-ion magnet sulfonate but also a ″magnetic anisotropic metal ion-organosulfonate-coordinated water″ approach for the design and preparation of bifunctional metalo-hydrogen-bonded organic framework (MHOF) materials.

Concurrent activation and conversion of N₂ and CO₂ are of significance yet face numerous obstacles due to the large dissociation energies of N≡N and C═O bonds. Utilizing a specifically developed reflectron time-of-flight mass spectrometer, we investigated the dual activation of N₂ and CO₂ mediated by copper and silver ions under ambient conditions. Isotope experiments identified that both N₂ and CO₂ can be effectively activated to generate a N-O coupling product (NO⁺), especially in the presence of copper ions, and the NO⁺ product attains the maximum intensity with an N₂/CO₂ ratio of 1:2, which validates a three-molecule reaction mechanism, namely, N₂ + 2CO₂ → 2NO + 2CO. Through detailed analyses of thermo-dynamics and reaction dynamics, we illustrate the Cu⁺-catalyzed three-molecule reaction mechanism for N-O coupling, validating the dual activation of N₂ and CO₂ simply by plasma-assisted single-ion catalysis.

Cancer presents a significant global public health challenge that impacts millions of individuals worldwide. The incorporation of natural products into cancer treatment has the potential to mitigate many of the side effects commonly associated with chemotherapy. This study builds on the advantages of enhancing the anticancer activity of natural flavonoids through metal chelation by synthesizing a natural antioxidant flavonoid complex, termed Lu-Mn nanozyme, which involves the chelation of luteolin with manganese ions. In vitro experiments demonstrated that Lu-Mn exhibits a strong affinity for hydrogen peroxide (H₂O₂) and effectively catalyzes the generation of hydroxyl radicals (•OH) from H₂O₂ within the tumor microenvironment. The administration of the Lu-Mn nanozyme not only induced apoptosis in tumor cells by upregulating the expression of cleaved caspase3 and caspase9 but also activated ferroptosis through downregulation of the NRF2-GPX4 signaling pathway. Furthermore, animal studies have shown that Lu-Mn possesses significant antitumor efficacy and a favorable safety profile. Collectively, these findings suggest that luteolin, through its chelation with metal ions, has considerable potential for application in cancer treatment.

Exploring electrolyte formulations that can effectively reduce the plating/stripping potentials of metallic electrodes holds great significance in advancing the development of high-voltage redox flow batteries. In this study, we introduce a novel Sn-based chelated electrolyte, namely, Sn(P₂O₇)₂^6-, by directly reacting the Sn²⁺ solution with an excess of P₂O₇^4- solution. Electrochemical tests prove that the incorporation of high-concentration P₂O₇^4- ligands could shift the plating/stripping potential to -0.67 V. Thus, the demonstrated Sn-I flow battery reveals an average cell voltage of nearly 1.2 V and maintains stable cycling over 250 cycles at a high current density of 80 mA cm^-2, with an average energy efficiency of about 70%. Moreover, no dendrite formation formed during the Sn deposition on the carbon felt. This study offers broad prospects for the future development of high-voltage Sn-based flow batteries.

Organic-inorganic hybrid Sn(IV)-based metal halides have received wide attention due to their excellent structural stability. However, realizing red-emitting Sn(IV)-based metal halides with high stability and efficient photoluminescence (PL) efficiency remains challenging. Here, a stable organic-inorganic Sn(IV)-based metal halide (C₈H₁₀O₂N)₂SnCl₆ with a zero-dimensional (0D) structure has been obtained, which, however, displays poor PL properties due to the inert expression of Sn⁴⁺-4d¹⁰ electrons and the intrinsic indirect band gap feature. To address the above challenges, Te⁴⁺ with an active 5s² lone pair is embedded into the lattice of (C₈H₁₀O₂N)₂SnCl₆, and as a result, 5%Te⁴⁺-doped (C₈H₁₀O₂N)₂SnCl₆ with a direct band gap exhibits a broadband deep-red emission (∼688 nm) with a high PL efficiency (∼53%). Experimental and calculated results reveal that the embedding of Te⁴⁺ can effectively regulate the band structure of (C₈H₁₀O₂N)₂SnCl₆ to facilitate the transformation from an indirect to a direct band structure, thereby leading to efficient radiative recombination. Benefiting from the above merits, a high-efficiency white light-emitting diode (WLED) has been fabricated using Te⁴⁺-doped (C₈H₁₀O₂N)₂SnCl₆ with an ultrahigh color rendering index (CRI) of up to 94.5, suggesting the great potential of this material for solid-state lighting. This work provides significant insight into the design of highly efficient red-emitting phosphors for organic-inorganic hybrid metal halides.