Dalton Transactions最新文献

Triple-negative breast cancer (TNBC) is an aggressive disease with limited treatment options due to the absence of ER, PR, and HER2 receptors. This review summarises the recent progress in the use of ruthenium, iridium, and rhenium complexes as alternative therapeutic agents for TNBC. These metal complexes are designed to respond to tumor-specific biomarkers or the tumor microenvironment, enabling selective uptake and enhanced anticancer activity. Through redox reactions and light activation, they generate reactive oxygen species, disrupt mitochondrial function, and induce cancer cell death. Overall, ruthenium, iridium, and rhenium complexes offer a multi-mechanistic and targeted approach that may help overcome resistance and improve future TNBC treatment strategies.

The construction of porous organic phenanthroline-based polymers without functional groups is meaningful but also challenging, as they could offer a novel, single-site, stable platform for diverse catalytic applications. In this study, a unique strategy was devised to construct porous organic phenanthroline-based polymers (POP-Phen-X) without reactive/coordinating functional groups in the polymer skeleton. The polymers POP-Phen-X with high BET surface areas were synthesized using a solvent knitting Friedel-Crafts polymerization method. The well-defined and isolated phenanthroline sites of POP-Phen-X can serve as a platform for the immobilization of metal catalysts via coordination bonds. The post-synthetic metalation of POP-Phen-A with palladium(II) acetate afforded a selective heterogeneous Pd catalyst for the cyanation of aryl halides. The resulting Pd/POP-Phen-A exhibited effective catalytic performance towards the cyanation of aryl halides with a TON of 200 and good recyclability.

Tris(2-pyrimidyl)- and tris(5-pyrimidyl)phosphines, previously inaccessible multidentate ligands, have been synthesized and introduced into coordination chemistry. Theoretical studies indicate that both ligands are weak σ-donors and strong π-acceptors, exhibiting electronic properties comparable to those of trialkyl phosphites. Positional isomerism of the pyrimidyl groups induces a pronounced difference in steric profile, with the 5-isomer adopting a more open conformation and the 2-isomer a significantly more compact geometry, reflected in their Tolman cone angles of 157° and 148°, respectively. Reactions with Cu(I), Cu(II), Ag(I), Au(I), Co(II), and Pt(II) salts afforded a series of molecular complexes together with 1D and 2D coordination polymers. Tris(5-pyrimidyl)phosphine acts predominantly as a P-monodentate or P,N-/N,N'-bridging ligand, yielding extended frameworks, whereas tris(2-pyrimidyl)phosphine forms both discrete complexes and coordination polymers through P,N,N'- and P,N,N',N″-modes. Selected Cu(I) and Ag(I) complexes exhibit short-lived luminescence with emission maxima between 460 and 605 nm. These findings demonstrate the potential of symmetric tris(pyrimidyl)phosphines as versatile ligands for coordination chemistry.

With the aim of investigating whether the coordination of fenamates to Ni(II) affects the biological profile, a chloro-derivative of fenamic acid (4'-chloro-fenamic acid) was synthesized and used as a ligand for the synthesis of seven nickel(II) complexes in the absence or presence of the nitrogen-donors pyridine, β-picoline, 1H-imidazole, 1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline, and 2,2'-bipyridylamine. The characterization of the resultant Ni(II) complexes was performed with diverse techniques (elemental analysis, molar conductivity measurements, mass spectrometry, IR and UV-vis spectroscopy, and single-crystal X-ray crystallography). The compounds were evaluated for their in vitro biological activity in terms of the antioxidant activity via free radical scavenging and H₂O₂ reduction, the antimicrobial activity against two Gram-positive and two Gram-negative bacterial strains, the interaction with calf-thymus DNA, the cleavage of supercoiled pBR322 plasmid DNA (pDNA) in the dark or under UVB/UVA/visible light irradiation, and the binding affinity toward bovine and human serum albumins. The antioxidant activity of the compounds is noteworthy against 2,2'-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid) radicals and H₂O₂, and comparable with that of the reference compounds. The complexes exhibit notable antimicrobial activity against the strains tested. The compounds interact with calf-thymus DNA via intercalation with binding constants of 10⁵-10⁶ M^-1 magnitude. The pDNA-cleavage ability of the compounds is significantly enhanced under irradiation. All the compounds can bind tightly and reversibly to both albumins tested.

The reactivity of the sodium phosphido-borane complex, [Na(THF)₃]⁺[1-BCy₂-8-PPh-C₁₀H₆]^- (1), with RCH₂NC isocyanides is reported. In contrast to traditional bases or phosphides, 1 act as an efficient nucleophile to form reactive carbanion intermediates instead of proton abstraction from RCH₂NC and formation of protonated phoshane 1-BCy₂-8-P(H)Ph-C₁₀H₆ (2). This study showed that 1 acts as a nucleophile and reacts with RCH₂NC in a 1 : 2 stoichiometry to form a 2-imidazoline, imidazole or an enamine. Isolated compounds demonstrate the ability of 1 in promoting carbanion formation and participating in subsequent reactions to give various N-substituted alkyl phosphine organic compounds, which are not usually obtained by different synthetical approaches.

In this study, a one-dimensional (1D) numerical simulation framework based on COMSOL Multiphysics was employed to investigate and optimize the structural design of a lead-free PSC. To optimize the device performance, the thickness of the ETL, absorber layer, and HTL was systematically varied, and its influence on the PV characteristics was investigated under standard operating conditions. Furthermore, the effects of operating temperature, donor concentration, and acceptor concentration on the electrical and PV behavior of the PSC were comprehensively examined. The simulation results demonstrated that the device performance was strongly influenced by both structural and material parameters. The highest PCE of approximately 19.565%, together with a P_max value of 195.650 W m^-2 and a J_sc value of 29.39 mA cm^-2, was achieved at an operating temperature of 285 K when the device temperature was varied between 285 K and 325 K. In addition, the maximum FF of 88.343% and a V_oc value of 1.012 V were obtained for a 50 nm-thick CsSnI₃ absorber layer. These findings highlight the critical role of optimizing layer thicknesses and operating conditions in augmenting the PV performance of lead-free PSCs. Overall, the present simulation offers valuable insights into the design and optimization of environmentally benign, low-cost, and lead-free PSCs. The optimized Mg-ZnO/CsSnI₃/GO device architecture demonstrates considerable potential for achieving high PV performance while addressing the toxicity concerns associated with lead-based perovskite materials.