五元杂环桥联结构调控的分子内电荷交互作用  

The Intramolecular Electronic Interaction Regulated by Five-membered Heterocycle Spacer Structure

作　　者：胡宇强[1] 王娜 韩利民[1] Hu Yuqiang;Wang Na;Han limin(Chemical Engineering College,Inner Mongolia University of Technology,Hohhot,010051;Department of Chemistry,Baotou Teachers’College,Baotou,014030)

机构地区：[1]内蒙古工业大学化学工程学院,呼和浩特010051 [2]包头师范学院化学系,包头014030

出　　处：《化学通报》2021年第12期1362-1369,1249,共9页Chemistry

基　　金：国家自然科学基金项目(22065028);内蒙古自治区自然科学基金项目(2017MS(LH)0202);内蒙古高校自然科学基金项目(NJZY17102)资助。

摘　　要：研究五元杂环桥联基团对分子内电荷传递调控规律是开发功能分子材料的基础。本文通过环合反应制备了9个2,5-双二茂铁基五元杂环衍生物作为模型分子。通过元素分析、红外光谱、质谱和核磁共振等手段对化合物结构进行了表征,采用循环伏安法和密度泛函量化模拟计算研究了分子内电荷传递与五元杂环桥联结构间的调控关系,发现这些化合物二茂铁间电荷交互作用随着桥联基团中杂原子数量的增加而减小,分子内电荷选择短程杂原子桥作为传输通道,桥联结构对二茂铁间电荷传递发挥着重要的调控作用。The study of the intramolecular electronic interaction of five-membered heterocycle(spacer)is the basis of developing functional molecular materials.In this work,nine 2,5-diferrocenyl five-membered heterocyelie molecules are synthesized as models to investigate the effect of intramolecular electron-transfer properties systematically.The synthesized compounds were characterized by elemental analysis,FT-IR,MS and NMR.The intramolecular electronie interactions regulated by spacer structure investigated through cyelie voltammetry in combination with density functional theory calculations.The results revealed that their electronic interaction decreases with the increase of heteroatoms in central heterocyele spacer;the intramolecular electronic interaction selects the short-range heteroatomic bridge as the transport channel and the electron-transfer property can be regulated by central heterocycle spacer structure.

关 键 词：双二茂铁 五元杂环 分子内电荷交互作用 

分 类 号：O627.81[理学—有机化学]