核磁共振波谱法表征 DAST 分子结构

庞子博*; 孟大磊; 窦瑛; 马思睿; 武聪; 程红娟; 徐永宽

doi:10.11938/cjmr20150409

波谱学杂志 >

2015 , Vol. 32 >Issue 4: 637 - 647

DOI: https://doi.org/10.11938/cjmr20150409

研究论文

核磁共振波谱法表征 DAST 分子结构

庞子博* ,
孟大磊 ,
窦瑛 ,
马思睿 ,
武聪 ,
程红娟 ,
徐永宽

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中国电子科技集团公司第四十六研究所，天津 300220

庞子博(1984-)，男，天津人，博士，工程师，有机晶体与复合材料专业，电话： 022-83870165， E-mail： hakky@126.com. *通讯联系人.

收稿日期: 2014-09-23

修回日期: 2015-10-23

网络出版日期: 2015-12-05

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Characterization of Molecular Structure of DAST Using Nuclear Magnetic Resonance Spectroscopy

PANG Zi-bo* ,
MENG Da-lei ,
DOU Ying ,
MA Si-rui ,
WU Cong ,
CHENG Hong-juan ,
XU Yong-kuan

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No. 46 Research Institute of China Electronics Technology Group Corporation, Tianjin 300220, China

*Corresponding author： PANG Zi-bo, Tel: +86-22-83870165, E-mail: hakky@126.com

Received date: 2014-09-23

Revised date: 2015-10-23

Online published: 2015-12-05

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摘要

DAST 晶体（即 4-N, N-二甲胺基-4’-N’-甲基-氮杂芪的对甲苯磺酸盐晶体）具有优良的二阶非线性光学性能和电光效应特性，可用于红外至太赫兹波段辐射与检测领域．为了表征 DAST 源粉分子结构及纯度，选择 CD₃OD 和 DMSO-d₆ 两种溶剂分别对 DAST 源粉进行了¹H NMR、 ¹³C NMR、 ¹H-¹H COSY、 HSQC 和 HMBC 表征．通过对谱峰的归属及分析发现， DAST 在 CD₃OD 溶液中倾向于以离子对状态存在，而在 DMSO-d₆ 溶液中倾向于以解离状态存在，并根据谱峰的变化推测了 DAST 在从 CD₃OD 溶液环境向 DMSO-d₆ 溶液环境变化时解离过程中电子云在共轭结构上重新分布的规律和骨架的变化情况．

关键词： 液体核磁共振(liquid-state NMR); 归属; 2D NMR; DAST; 太赫兹

本文引用格式

庞子博* , 孟大磊 , 窦瑛 , 马思睿 , 武聪 , 程红娟 , 徐永宽 . 核磁共振波谱法表征 DAST 分子结构[J]. 波谱学杂志, 2015 , 32(4) : 637 -647 . DOI: 10.11938/cjmr20150409

Abstract

DAST crystal (4-N, N-dimethylamino-4’-N’-methyl-stilbazolium tosylate crystal) shows electro-optical effect, and has excellent properties for second-order nonlinear optics. It can be used for wave radiation and detection from infrared to terahertz range. In this study, the molecular structure and purity of DAST crystal were analyzed by liquid-state NMR spectroscopy (i.e., ¹H NMR, ¹³C NMR, ¹H-¹H COSY, HSQC and HMBC) using CD₃OD and DMSO-d₆ as solvents. It was observed that DAST tended to exist in the form of ion pair in CD₃OD solution, while in the form of dissociative state in DMSO-d₆solution. This could be due to solvent-dependent redistribution of electron cloud in the conjugated structure and movement of the framework.

Key words： liquid-state NMR; assignment; two-dimensional NMR; DAST; terahertz

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