Mechanistic study of the bismuth mediated fluorination of arylboronic esters and further rational design.

Density functional theory (DFT) calculations have been performed to gain insight into the catalytic mechanism of the bismuth redox catalyzed fluorination of arylboronic esters to deliver the widely used arylfluoride compounds ( 2020, , 313-317). The study reveals that the whole catalysis can be characterized three stages: (i) transmetallation generates the Bi(iii) intermediate 5, capitalizing on the use of KF as an activator. (ii) 5 then reacts with the electrophilic fluorination reagent 1-fluoro-2,6-dichloropyridinium 4 oxidative addition to give the Bi(v) intermediate IM4A.

A Bis-(carbone) Pincer Ligand and Its Coordinative Behavior toward Multi-Metallic Configurations.

Carbones are divalent carbon(0) species that contain two lone pairs of electrons. Herein, we have prepared the first known stable and isolable free bis-(carbone) pincer framework with a well-defined solid-state structure. This bis-(carbone) ligand is an effective scaffold for forming monometallic (Ni and Pd) and trinuclear heterometallic complexes with Au-Pd-Au, Au-Ni-Au, and Cu-Ni-Cu configurations.

Synthesis, characterization, and photoluminescence properties of three two-dimensional lanthanide-containing Dawson-type polyoxometalates.

Three [α2-P2W17O61]10--based lanthanide-containing polyoxometalates (LCPs) [N(CH3)4]3H8{Ln(H2O)7[Ln(H2O)3Ln(H2O)4(α2-P2W17O61)2]}·48H2O [Ln = La3+ (1), Ce3+ (2), and Pr3+ (3)] were successfully obtained by the reaction of a trivacant Dawson-type precursor [P2W15O56]12- and lanthanide ions under hydrothermal conditions. The compounds 1-3 were fully characterized by single-crystal X-ray diffraction and a series of analytical methods, including elemental analyses, powder X-ray diffraction (PXRD), IR spectroscopy, Raman spectroscopy, UV/vis diffuse reflectance spectroscopy, and thermogravimetric analysis (TGA). Single-crystal X-ray diffraction analyses indicated that 1-3 were isostructural and exhibited a 2D network architecture through the alternative connection of [α2-P2W17O61]10- and lanthanide ions.

Well-tuned white-light-emitting behaviours in multicenter-Ln polyoxometalate derivatives: A photoluminescence property and energy transfer pathway study.

White light-emitting diodes (WLEDs) are of scientific significance in terms of their wide applications, and few uminescent materials based on white-light-emitting polyoxometalate (POM) derivatives have been reported till now. Herein, a series of organic chromophores modified POM derivatives [N(CH)]KLn(CHO)(HO)(α-PWO)]·11HO (Ln = Eu (1), Tb (2), Tm (3), Lu (4)) and multicenter-Ln analogues [N(CH)]KEuTbTm(CHO)(HO)(α-PWO)·11HO (5-11) were synthesized successfully and were characterized by various physico-chemical analysis. The investigations indicate the white-light-emitting behavior can be well tuned by adjusting the molar ratio of Eu/Tb/Tm = 0.

Elucidating white light emissions in Tm/Dy codoped polyoxometalates: a color tuning and energy transfer mechanism study.

The double-tartaric bridging Tm-substituted POM derivative [N(CH3)4]6K3H7[Tm(C4H2O6)(α-PW11O39)]2·27H2O (1) was successfully synthesized and well characterized by various physico-chemical analyses. Furthermore, the mixed Dy3+/Tm3+ ion-based POM derivatives [N(CH3)4]6K3H7[DyxTm1-x(C4H2O6)(α-PW11O39)]2·27H2O (3-8) were first synthesized and confirmed by PXRD and IR spectra, indicating compounds 3-8 are isomorphic with 1. The detailed analyses of Ln-O-W bond angle and coordinated aqua ligands around emitting Ln3+ ions have revealed that the mentioned negative factors do not effectively affect the luminescence of emitting Ln3+ ions in 1-8.