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Tetralithio Metalla-aromatics with Two Independent Perpendicular Dilithio Aromatic Rings Spiro-fused by One Manganese Atom
No full textHerein, we present the realization of a class of unprecedented aromatic structures 2: metalla-aromatics with two independent and perpendicular aromatic rings spiro-fused by a transition-metal spiro atom, of which their corresponding organic analogues are impossible. Tetralithio spiro manganacycles 2 are readily synthesized from 1,4-dilithio-1,3-butadienes 1 and MnCl2 in the presence of lithium. The aromaticity of 2 is supported by experimental measurements (X-ray structural analysis, NMR) and theoretical analyses (NICS, ACID, MOs). The spiro atom Mn in 2 uses its 3d(xz) and 3d(xy) orbitals to form the two perpendicular manganacycles, which are two independent 6 pi aromatic systems. Theoretical analyses reveal that the Li cations play an indispensable role in governing their geometric and electronic structures and hence their aromaticity. Therefore, this work contributes not only to enrich the concept of aromaticity, but also to deepen the understanding of the fundamental chemical bonding
Syntheses, Structural Characterizations and Spectroscopic Properties of Two Copper(I) Complexes Based on Diphosphine Ligands and [2,3-f]pyrazino[1,10]phenanthroline
No full textTwo novel copper(I) complexes [Cu(dppBz)(dpq)]ClO4 (1) and [Cu(dppe)(dpq)]ClO4 (2) (dppBz=1,2-bis (diphenylphosphino)benzene, dppe=1,2-bis(diphenylphosphino)ethene, dpq=[2,3-f]pyrazino[1,10]phenanthroline) have been synthesized and characterized by X-ray diffraction, elemental analysis, infrared spectroscopy, absorption spectra, luminescent spectra, 11-1 NMR, 31P NMR spectroscopy and terahertz (THz) time-domain absorption spectroscopy. The central Cu(I) ion is chelated by a diimine ligand and a diphosphine ligand forming a distorted tetrahedron configuration for 1, and the configuration of 2 is similar to 1. The luminescent spectra of 2 indicated that the emission has metal-to-ligand charge transfer (MLCT) characteristics. The terahertz time-domain absorption spectroscopy analysis in a range of 0.2-2.8 THz showed that the absorption peaks at 0.40-0.90 THz are related to the coordination of the central Cu(I). CCDC: 1874580, 1; 1874581, 2
White Photoluminescent Ti3C2 MXene Quantum Dots with Two-Photon Fluorescence
No full textA recently created class of inorganic 2D materials, MXenes, has become a subject of intensive research. Reducing their dimensionality from 2D to 0D quantum dots (QDs) could result in extremely useful properties and functions. However, this type of research is scarce, and the reported Ti3C2 MXene QDs (MQDs) have only shown blue fluorescence emission. This work demonstrates a facile, high-output method for preparing bright white emitting Ti3C2 MQDs. The resulting product is two layers thick with a lateral dimension of 13.1 nm. Importantly, the as prepared Ti3C2 MQDs present strong two-photon white fluorescence. Their fluorescence under high pressure is also investigated and it is found that the white emission is very stable and the pressure makes it possible to change from cool white emission to warm white emission. Hybrid nanocomposites are then fabricated by polymerizing Ti3C2 MQDs in polydimethylsiloxane (PDMS) solution, and the bright white emitting hybrid materials in white light-emitting diodes are used. This work provides a facile and general approach to modulate various nanoscale MXene materials, and could further aid the wide development of applications for MXene materials in various optical-related fields