.png){kind=icon}
返回
Macrocyclic Chromium(III) Catecholate Complexes
.png){kind=icon}
PRE
AI
DOI：10.1021/acs.inorgchem.0c03224.png)
.png){kind=icon}
原文求助.png){kind=icon}
分享.png){kind=icon}
收藏
摘要
En 中文
The synthesis and structural, electrochemical, spectroscopic, and magnetic characterizations of Cr-III(HMC) catecholate and semiquinonate complexes are reported herein, where HMC is 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane. cis-[Cr-(HMC)(Cat)](+) complexes (Cat = catecholate, [1](+); tetrachlorocatecholate, [2](+); and 3,5-di-tert-butylcatecholate, [3](+)) were prepared from the reaction between appropriate catechol and [Cr-III(HMC)-Cl-2]Cl reduced in situ by zinc. Chemical oxidation of [3](+) by FcPF(6) resulted in cis-[Cr(HMC)(SQ)](2+) ([3](2+), SQ = 3,5-di-tert-butyl-semiquinonate). Single crystal X-ray diffraction studies revealed the cis-chelation of the Cat/SQ ligand around the Cr metal center and confirmed the Cat/SQ nature of the ligands. Reversible oxidations of Cat to SQ were observed in the cyclic voltammograms of [1](+)-[3](+), while the Cr-III center remains redox inactive. The absorption spectrum of the SQ complex [3](2+) exhibits an intense spin-forbidden transition in solution. Time-delayed phosphorescence spectra recorded at 77 K revealed that all catecholate complexes emit from the E-2 state, while [2](+) also emits from the T-2(1) state. Temperature-dependent magnetic susceptibility measurements indicate the Cat complexes exist as S = 3/2 systems, while the SQ complex behaves as an S = 1 system, resulting from strong antiferromagnetic coupling of the S = 3/2 Cr center with the S = 1/2 SQ radical. Density functional theory (DFT) shows the similarities between the SOMOs of [1](+) and [2](+) and differences in their LUMOs in the ground state.
Keyword:
TRANSITION-METAL-COMPLEXES
COORDINATION-COMPOUNDS
ELECTRON-TRANSFER
RADICAL LIGANDS
O-AMINOPHENOL
PHOTOPHYSICS
ADDUCTS
VALENCE
PHOTOCHEMISTRY
REACTIVITY
AI总结
对已上传原文的论文进行重点信息的提取，主要内容包括：简要概述、研究摘要、背景介绍、关键亮点、图文解析、展望与总结。
期刊
IF:
4.7
论文数:
4.9W
被引数:
10.5W
机构
引用论文
Self-assembly of five new organic–inorganic hybrids based on two new flexible tricationic templates基于两个新的柔性三阳离子模板的五个新的有机-无机杂化物的自组装
PREAI
分享收藏
SanG, a transcriptional activator, controls nikkomycin biosynthesis through binding to the sanN–sanO intergenic region in Streptomyces ansochromogenes.png)
Microbiology
OAAI
MicrobiologyIF0
OAAI分享收藏A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu94元素h-pu的密度泛函色散校正 (dft-d) 的一致且精确的从头算参数化
PREAI
分享收藏
查看更多内容