DITFB/4-OH-TEMPO体系中卤键作用的19F DNP研究

doi:10.11938/cjmr20172557

波谱学杂志 ›› 2017, Vol. 34 ›› Issue (4): 421-428.doi: 10.11938/cjmr20172557

DITFB/4-OH-TEMPO体系中卤键作用的¹⁹F DNP研究

高珊^1,2, 黄重阳², 张震², 陈俊飞², 贺玉贵², 陈黎², 陈方², 张金枝¹, 刘朝阳²

1. 湖北大学化学化工学院, 湖北武汉 430062;
2. 波谱与原子分子物理国家重点实验室, 武汉核磁共振中心(中国科学院武汉物理与数学研究所), 湖北武汉 430071

收稿日期:2017-01-23 修回日期:2017-11-01 出版日期:2017-12-05 发布日期:2017-11-29
通讯作者: 张金枝,Tel:027-88662747,E-mail:zhangjinzhi2000@yahoo.com.cn;刘朝阳,Tel:027-87198790,E-mail:chyliu@wipm.ac.cn E-mail:zhangjinzhi2000@yahoo.com.cn;chyliu@wipm.ac.cn
基金资助:
国家自然科学基金资助项目（11575287，11405264）.

The Effect of Intermolecular Halogen Bond on ¹⁹F DNP Enhancement in 1, 4-Diiodotetrafluorobenzene/4-OH-TEMPO Supramolecular Assembly

GAO Shan^1,2, HUANG Chong-yang², ZHANG Zhen², CHEN Jun-fei², HE Yu-gui², CHEN Li², CHEN Fang², ZHANG Jin-zhi¹, LIU Chao-yang²

1. Faculty of Chemistry and Material Science, Hubei University, Wuhan 430062, China;
2. State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, National Center for Magnetic Resonance in Wuhan(Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences), Wuhan 430071, China

Received:2017-01-23 Revised:2017-11-01 Online:2017-12-05 Published:2017-11-29

摘要/Abstract

摘要： 卤键与氢键相似，是实现分子与分子非共价键连接的作用之一，其广泛地应用于工程材料和生命化学等领域．有关卤键相互作用的动态核极化（DNP）研究还未见报道．本文利用连续波-电子顺磁共振（CW-EPR）谱仪及自主研制的DNP实验平台对存在卤键相互作用的体系——1，4-二碘四氟苯（DITFB）/4-羟基-2，2，6，6-四甲基吡啶-1-氧自由基（4-OH-TEMPO）进行¹⁹F DNP研究，并与无卤键作用对照组——六氟苯（PFB）/4-OH-TEMPO的¹⁹F DNP增强效果进行了比较．结果发现，DITFB/4-OH-TEMPO较PFB/4-OH-TEMPO具有更窄的EPR线宽和更大的¹⁹F DNP增强．这表明自由基与DITFB卤键作用削弱了自由基之间的电子自旋-自旋相互作用，从而使自由基横向弛豫时间（T_2e）增加、线宽变窄，导致DNP饱和因子和增强倍数变大．因此，可以通过卤键调控自由基电子自旋相互作用，以改善核的DNP增强效果．

关键词: ¹⁹F动态核极化(¹⁹F DNP), 卤键, 1,4-二碘四氟苯(DITFB)/4-羟基-2,2,6,6-四甲基吡啶-1-氧自由基(4-OH-TEMPO), DNP增强

Abstract: Halogen bond, as hydrogen bond, is a non-covalent bond. Dynamic nuclear polarization (DNP) technique has been used previously to study hydrogen bonds-mediated intermolecular interactions. However, no study has been carried out so far to study the halogen bond-mediated intermolecular interactions with DNP. In this work, ¹⁹F DNP polarization efficiency of the halogen bonds existing in supramolecular assembling by 4-OH-TEMPO and 1,4-diiodotetrafluorobenzene (DITFB) was studied on a home-made DNP system. The formation of intermolecular halogen bonds appeared to increase ¹⁹F DNP polarization efficiency, suggesting that the spin-spin interactions among electrons were weakened by the halogen bonds, resulting in an increased T_2e and a larger saturation factor.

Key words: ¹⁹F DNP, halogen bond, DITFB/4-OH-TEMPO, DNP enhancement

中图分类号:

O482.53

高珊, 黄重阳, 张震, 陈俊飞, 贺玉贵, 陈黎, 陈方, 张金枝, 刘朝阳. DITFB/4-OH-TEMPO体系中卤键作用的¹⁹F DNP研究[J]. 波谱学杂志, 2017, 34(4): 421-428.

GAO Shan, HUANG Chong-yang, ZHANG Zhen, CHEN Jun-fei, HE Yu-gui, CHEN Li, CHEN Fang, ZHANG Jin-zhi, LIU Chao-yang. The Effect of Intermolecular Halogen Bond on ¹⁹F DNP Enhancement in 1, 4-Diiodotetrafluorobenzene/4-OH-TEMPO Supramolecular Assembly[J]. Chinese Journal of Magnetic Resonance, 2017, 34(4): 421-428.

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DITFB/4-OH-TEMPO体系中卤键作用的¹⁹F DNP研究

The Effect of Intermolecular Halogen Bond on ¹⁹F DNP Enhancement in 1, 4-Diiodotetrafluorobenzene/4-OH-TEMPO Supramolecular Assembly

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