• 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>Chemistry: A European journal >Experimental and Computational Studies of a Multi-Electron Donor-Acceptor Ligand Containing the Thiazolo[5,4-d] thiazole Core and its Incorporation into a Metal-Organic Framework
【24h】

Experimental and Computational Studies of a Multi-Electron Donor-Acceptor Ligand Containing the Thiazolo[5,4-d] thiazole Core and its Incorporation into a Metal-Organic Framework

机译：含噻唑并[5,4-d]噻唑核的多电子供体-受体配体的实验和计算研究及其在金属-有机骨架中的结合

获取原文
获取原文并翻译 | 示例
           
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

A ligand containing the thiazolo[5,4-d] thiazole (TzTz) core (acceptor) with terminal triarylamine moieties (donors), N,N'-(thiazolo[5,4-d] thiazole-2,5-diylbis(4,1-phenylene)) bis(N-(pyridine-4-yl) pyridin-4-amine (1),was designed as a donor-acceptor system for incorporation into electronically active metal-organic frameworks (MOFs). The capacity for the ligand to undergo multiple sequential oxidation and reduction processes was examined using UV/Vis-near-infrared spectroelectrochemistry (UV/Vis-NIR SEC) in combination with DFT calculations. The delocalized nature of the highest occupied molecular orbital (HOMO) was found to inhibit charge-transfer interactions between the terminal triarylamine moieties upon oxidation,whereas radical species localized on the TzTz core were formed upon reduction. Conversion of 1 to diamagnetic 2+ and 4+ species resulted in marked changes in the emission spectra. Incorporation of this highly delocalized multi-electron donor-acceptor ligand into a new two-dimensional MOF,[Zn(NO3)(2)(1)](2),resulted in an inhibition of the oxidation processes,but retention of the reduction capability of 1. Changes in the electrochemistry of 1 upon integration into 2 are broadly consistent with the geometric and electronic constraints enforced by ligation.
机译：含有噻唑并[5,4-d]噻唑（TzTz）核（受体）和末端三芳基胺基团（供体），N，N'-（噻唑并[5,4-d]噻唑-2,5-diylbis（ 4,1-亚苯基））双（N-（吡啶-4-基）吡啶4-胺（1）被设计为供体-受体体系，可并入电子活性金属-有机骨架（MOF）中。结合紫外/可见-近红外光谱电化学（UV / Vis-NIR SEC）和DFT计算，对配体经历了多个顺序的氧化和还原过程进行了研究，发现了最高占据分子轨道（HOMO）的离域性质为了抑制端基三芳基胺部分之间的电荷转移相互作用，在氧化时会还原形成TzTz核上的自由基，将1转变为反磁性2+和4+会导致发射光谱发生明显变化。高度离域的多电子供体-受体配体进入新的tw o维MOF [Zn（NO3）（2）（1）]（2）抑制了氧化过程，但保留了1的还原能力。整合到2中后1的电化学变化是与结扎所施加的几何和电子约束条件基本一致。

著录项

相似文献

  • 外文文献
  • 中文文献
  • 专利
获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号