Three ruthenium(II) polypyridyl complexes with 5-amino-1,10-phenanthroline ligands have been successfully designed and synthesized. They have been fully characterized by ESI-MS, ESI-HRMS, 1H NMR, and elemental analyses. The photophysical and electrochemical properties of the three complexes have been investigated in organic solvent. The geometrical configuration and the electron density distribution in the frontier molecular orbitals of the three complexes have been studied. The three complexes show metal-to-ligand charge transfer (1MLCT) absorption at 445 nm, and intense triplet metal-to-ligand (3MLCT) emission at around 619 nm in fluid solution at 298 K and 580 nm in low-temperature glass. Electrochemical studies of the three complexes are consistent with one RuIII/II reversible couple at around 1.31 V accompanied by three ligand-centered reduction couples.
Luminescent seven-coordinated zirconium and hafnium complexes bearing three mono-anionic 2,2′-pyridylpyrrolide ligands and one chloride were synthesized. Solid-state structures and the dynamic behaviors in solution were probed by X-ray crystallography and variable temperature 1H NMR experiments, respectively. Absorption spectroscopy and time-dependent density functional theory (TD-DFT) calculations supported a hybrid of ligand-to-metal charge transfer (LMCT)/ligand-to-ligand charge transfer (LLCT) for the visible light absorption band. The complexes (MePMPMe)3MCl (M=Zr, Hf, MePMPMe=3,5-dimethyl-2-(2-pyridyl)pyrrolide) are emissive in solution at room temperature upon irradiation with visible light due to a combination of phosphorescence and fluorescence characterized by excited state lifetimes in the μs and low to sub-ns timescale, respectively. Electrochemical experiments revealed that the zirconium complex possesses a reversible redox event under highly reducing condition (−2.29 V vs. Fc+/0). 相似文献
The ester bond as a universal linker has recently been applied in gene delivery systems owing to its efficient gene release by electrostatic repulsion after its cleavage. However, the ester bond is nonlabile and is difficult to cleave in cells. This work reports a method in which a secondary amine was introduced to the β-position of the ester bond to generate a hydrogen-bond cyclization (HBC) structure that can make the ester bond hydrolysis ultrafast. A series of molecules comprising ultrasensitive esters that can be activated by H2O2 were synthesized, and it was found that those able to form an HBC structure showed complete ester hydrolysis within 5 h in both water and phosphate-buffered saline solution, which was several times faster than other methods reported. Then, a series of amphiphilic poly(amidoamine) dendrimers were constructed, comprising the ultrasensitive ester groups for gene delivery; it was found that they could effectively release genes under quite a low concentration of H2O2 (<200 μm ) and transport them into the nucleus within 2 h in Hela cells with high safety. Their gene transfection efficiencies were higher than that of PEI25k. The results demonstrated that the hydrogen-bond-induced ultrasensitive esters could be powerfully applied to construct gene delivery systems. 相似文献
Russian Journal of Organic Chemistry - New data since about 2010 concerning complex formation of phosphorus-containing cyclophanes and cryptands with transition metals, as well as guest-host... 相似文献
A graph is -choosable if the following holds: For any list assignment which assigns to each vertex a set of real numbers, and assigns to each edge a set of real numbers, there is a total weighting such that for , and for every edge . This paper proves that if is a connected graph of maximum degree , then is -choosable. 相似文献
Optics and Spectroscopy - Studies published in the period from 2014 to 2018 that are aimed at creating nondispersive and photoacoustic IR gas analyzers with LED radiation sources based on... 相似文献