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991.
A series of imidazolium chlorides for the formation of tridentate CNO‐donor palladium(II) complexes featuring N‐heterocyclic carbene moieties have been developed from cheap and readily available starting materials with high yields. Their palladium complexes were prepared by reactions between the ligand precursors and PdCl2 using K2CO3 as base in pyridine with reasonable yields. These air‐stable metal complexes were characterized using 1H NMR and 13C{1H} NMR spectroscopy and elemental analyses. Heteronuclear multiple bond correlation experiments were performed to identify key NMR signals of these compounds. The structures of two of the complexes were also established by single‐crystal X‐ray diffraction analysis. One of these complexes was successfully applied in the direct C―H functionalization reactions between heterocyclic compounds and aryl bromides, producing excellent yields of coupled products. The coupling reactions were scalable, allowing grams of coupled products to be obtained with a mere 2 mol% of Pd loading. The catalyst system developed allowed the large‐scale preparation of several push–pull chromophores straightforwardly. Photophysical properties based on UV–visible and fluorescence spectroscopy for these chromophores were investigated. Deep blue photoluminescence with moderate quantum efficiency and twisted intramolecular charge transfer excited state were observed for these chromophores. Density functional theory (DFT) and time‐dependent DFT calculations were performed to support the experimental results. 相似文献
992.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2018,130(39):12991-12995
Materials discovery enables both realization and understanding of new, exotic, physical phenomena. An emerging approach to the discovery of novel phases is high‐pressure synthesis within diamond anvil cells, thereby enabling in situ monitoring of phase formation. Now, the discovery via high‐pressure synthesis of the first intermetallic compound in the Cu‐Pb system, Cu3Pb is reported. Cu3Pb is notably the first structurally characterized mid‐ to late‐first‐row transition‐metal plumbide. The structure of Cu3Pb can be envisioned as a direct mixture of the two elemental lattices. From this new framework, we gain insight into the structure as a function of pressure and hypothesize that the high‐pressure polymorph of lead is a possible prerequisite for the formation of Cu3Pb. Crucially, electronic structure computations reveal band crossings near the Fermi level, suggesting that chemically doped Cu3Pb could be a topologically nontrivial material. 相似文献
993.
Two water‐soluble 6‐(pyrazin‐2‐yl)‐1,3,5‐triazine‐2,4‐diamino (pzta)‐based Cu(II) complexes, namely [Cu(l ‐Val)(pzta)(H2O)]ClO4 ( 1 ) and [Cu(l ‐Thr)(pzta)(H2O)]ClO4 ( 2 ) (l ‐Val: l ‐valinate; l ‐Thr: l ‐threoninate), were synthesized and characterized using elemental analyses, molar conductance measurements, spectroscopic methods and single‐crystal X‐ray diffraction. The results indicated that the molecular structures of the complexes are five‐coordinated and show a distorted square‐pyramidal geometry, in which the central copper ions are coordinated to N,N atoms of pzta and N,O atoms of amino acids. The interactions of the complexes with DNA were investigated using electronic absorption, competitive fluorescence titration, circular dichroism and viscosity measurements. These studies confirmed that the complexes bind to DNA through a groove binding mode with certain affinities (Kb = 4.71 × 103 and 1.98 × 103 M?1 for 1 and 2 , respectively). The human serum albumin (HSA) binding properties of the complexes were also evaluated using fluorescence and synchronous fluorescence spectroscopies, indicating that the complexes could quench the intrinsic fluorescence of HSA in a static quenching process. The relevant thermodynamic parameters revealed the involvement of van der Waals forces and hydrogen bonds in the formation of complex–HSA systems. Finally, molecular docking technology was also used to further verify the interactions of the complexes with DNA/HSA. 相似文献
994.
995.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(2):597-601
One‐electron reduction of a pyrazolate‐bridged triangular Fe3(μ3‐O) core induces a cascade wherein all three metal centers switch from high‐spin Fe3+ to low‐spin Fe2.66+. This hypothesis is supported by spectroscopic data (1H‐NMR, UV‐vis‐NIR, infra‐red, 57Fe‐Mössbauer, EPR), X‐ray crystallographic characterization of the cluster in both oxidation states and also density functional theory. The reduction induces substantial contraction in all bond lengths around the metal centers, along with diagnostic shifts in the spectroscopic parameters. This is, to the best of our knowledge, the first example of a one‐electron redox event causing concerted change in multiple iron centers. 相似文献
996.
997.
998.
Selective Exo‐Enzymatic Labeling of N‐Glycans on the Surface of Living Cells by Recombinant ST6Gal I
999.