基于光致变色的联茚满烯二酮衍生物的新型光调控磁性的分子基磁体的合成及性能

doi:10.6023/cjoc201602027

摘要/Abstract

分子基磁性材料，可用于信息存储、磁成像、光磁开关等. 因此，分子基磁体设计与合成一直是当今科学研究的热门课题. 受分子基磁体的启发，本研究合成了新型光调控磁性的分子基磁体含有2-硝基丙烷自由基和2，2，6，6-四甲基-1-氧基哌啶（TEMPO）自由基的联茚满烯二酮衍生物4. 化合物4的合成方法为，以光致变色的7，7'-二甲基-3，3'-二乙基-3，3'-二羟基-2，2'-二茚叉基-1，1'-二酮（1）为起始原料，经过溴代反应，得到7，7'-二（溴代甲基）-3，3'-二乙基-3，3'-二羟基-2，2'-二茚叉基-1，1'-二酮（2）. 化合物2和2-硝基丙烷在乙醇钠的乙醇溶液中反应得到含有2-硝基丙烷自由基和醛基的联茚满烯二酮衍生物3. 根据¹H NMR，MS和元素分析对化合物3的结构分析表明，2-硝基丙烷基团和化合物3苯环上的亚甲基相连. 对化合物3的¹H NMR和ESR波谱进一步的分析表明2-硝基丙烷基团上存在单电子自旋. 在化合物3的基础上，稳定的氮氧自由基TEMPO被成功地引入光致变色的联茚满烯二酮衍生物的苯环上得化合物4. 对化合物2，3和4光照前后的性质变化进行了研究. 固态化合物2，3和4光照下皆可发生光致变色；固态化合物2光照后可测得ESR波谱；固态化合物3和4光照前后皆可测得ESR波谱，且光照前后ESR波谱发生变化. 磁化率测试表明，固态化合物4光照前后皆具有反铁磁性，且光照后反铁磁相互作用增强. 测试结果表明固态化合物3和4光照后有两个或三个自旋中心，分别是2-硝基丙烷或TEMPO自由基以及光照产生的来自于联茚满烯二酮的羰基上的自由基. 固态化合物4的颜色和磁性可用光调控.

关键词: 联茚满烯二酮, 2-硝基丙烷自由基, 光控磁性, 光致变色, 分子基磁体

Molecular-based magnetic material can be used for information storage, magnetic imaging, photo-magnetic switching and so on. So the design and synthesis of the molecular-based magnet is a focus of contemporary science research. Sparked by the strategy of molecular magnets, the novel photomodulation magnetic molecular-based magnet photochromic biindenylidenedione derivative with 2-nitropropane radical and 2,2,6,6-tetramethyl-piperidinyloxy (TEMPO) radical (4) was synthesized. The synthetic method of compound 4 is that starting from photochromic biindenylidenedione derivative 7,7'-dimethyl-[2,2'-bi-1H-indene]-3,3'-diethyl-3,3'-di-hydroxy-1,1'-dione (1), via bromination reaction, 7,7'-bis(bromomethyl)- [2,2'-bi-1H-indene]-3,3'-diethyl-3,3'-dihydroxy-1,1'-dione (2) was obtained. Sodium ethoxide, 2-nitropropane and compound 2 were dissolved in absolute ethanol reaction to obtain biindenylidenedione derivative with 2-nitropropane radical and formyl 3. The structure of compound 3 was confirmed by ¹H NMR, MS and element analysis. The results indicated that 2-nitropropane group bonds with one methylene on the benzene ring of the compound 3. In further analysis to ¹H NMR and electron spin-resonace (ESR) spectra of compound 3 demonstrated that single electron spin exists in 2-nitropropane group. On the basis compound 3, stable nitroxide radical TEMPO was successfully introduced into the benzene rings of photochromic biindeny lidenedione derivative to obtain compound 4. The properties of compounds 2, 3 and 4 were investigated. The testing results display that the solid compounds 2～4 possess photochromic property. ESR spectrum was found when irradiated solid compound 2. ESR spectrum was found and changed before and after photoirradiation in solid state of compound 3 and 4. The magnetic susceptibility measurement shows that the antiferromagnetic interaction for before and after photoirradiation in solid state of compound 4, and the antiferromagnetic interaction becomes stronger after photoirradiation. These testing results demonstrated that after photoirradiation in solid state of compound 3 and 4, there are two or three kinds of spin centres after photoirradiation: one is 2-nitropropane or TEMPO radical, and another is photo-generated radical of two indanione moieties. The color and magnetic of the solid compound 4 can be photomodulated.

Key words: biindenylidenedione, 2-nitropropane radical, photomodulation magnetism, photochromism, molecular-based magnet

引用此文

陈勇, 孟继本. 基于光致变色的联茚满烯二酮衍生物的新型光调控磁性的分子基磁体的合成及性能[J]. 有机化学, 2016, 36(8): 1869-1877.

Chen Yong, Meng Jiben. Synthesis and Properties of Novel Photomodulation Magnetic Molecular-Based Magnet Based on Photochromic Biindenylidenedione Derivative[J]. Chin. J. Org. Chem., 2016, 36(8): 1869-1877.

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