无取代酞荭的高效制备及其新衍生物的研究

doi:10.6023/A20080389

化学学报 ›› 2021, Vol. 79 ›› Issue (1): 81-86.DOI: 10.6023/A20080389 上一篇下一篇

研究论文

无取代酞荭的高效制备及其新衍生物的研究

李凌燕^a, 郑玮^a^,^*(), 李承辉^a^,^*()

1 南京大学化学化工学院配位化学国家重点实验室南京 210093

投稿日期:2020-08-24 发布日期:2020-09-27
通讯作者: 郑玮, 李承辉
作者简介:
* E-mail: weizheng@nju.edu.cn; chli@nju.edu.cn
基金资助:
国家自然科学基金(21631006); 国家自然科学基金(21771100); 国家自然科学基金(21601060); 江苏省自然科学基金(BK20170016)

A Facile Synthetic Method and New Derivatives of Phthalorubines

Ling-Yan Li^a, Wei Zheng^a^,^*(), Cheng-Hui Li^a^,^*()

1 State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing National Laboratory of Microstructures, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210093, China

Received:2020-08-24 Published:2020-09-27
Contact: Wei Zheng, Cheng-Hui Li
Supported by:
the National Natural Science Foundation of China(21631006); the National Natural Science Foundation of China(21771100); the National Natural Science Foundation of China(21601060); the Natural Science Foundation of Jiangsu Province(BK20170016)

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摘要/Abstract

酞荭具有独特的稠环结构、光谱性质及多样的配位方式, 是一类颇具潜力的新兴材料. 在酞荭研究起步阶段, 无取代酞荭 Pr-2是研究反应与探索应用最重要的化合物. 然而目前制备 Pr-2的方法仅能基于 Pr-1的脱氰基反应. 该方法成本高昂并难以放大, 限制了酞荭类材料的后续研究与发展. 本工作利用Ni(II)催化剂替代昂贵的Rh(I), 高效制备 Pr-2, 且该方法可放大至十克级别, 产率超过50%. 同时, 在调整反应条件的过程中, 新生成氰基( Pr-1.5)与甲基( Pr-1.6)取代的酞荭化合物, 都展现出良好的平面性与π-π相互作用, 而不同取代基对酞荭的荧光性质有着重要的影响. 本论文所报道的工作, 尤其是便捷的合成方法对于酞荭的推广和应用具有极为重要而深远的意义.

关键词: 酞荭, 稠环, 脱氰基, 染料, 杂环

Phthalorubines ( Prs), a new series of fused-ring dyes, with novel planar structure, interesting synthetic mechanism, characteristic spectra properties and multiple coordinated patterns, have potential applications in different fields. During the start-up stage for phthalorubine research, a molecule without any substituents, such as Pr-2,is the most important compound for both synthetic studies and application exploration. Reported method to obtain Pr-2 is via decyanation of Pr-1, the first phthalorubine compound easily synthesized from phthalonitrile. However, the process of decyanation requires expensive Rh(I) complex as catalyst, which also make the reaction difficult to amplify. These disadvantages greatly limit follow-up studies of phthalorubines. A facile method to synthesize Pr-2could effectively accelerate the development and subsequent studies of phthalorubines. Herein, we reported a facile method to synthesize Pr-2via Ni(II) catalyzed process with high yield of 58%, while this method could be amplified to more than 10 grams. Moreover, during the process of tuning reaction conditions, two new kinds of phthalorubines were detected, with cyano group ( Pr-1.5) and methyl group ( Pr-1.6), respectively. According to the results of different conditions, Pr-1.5 is the key intermediate product from Pr-1 to Pr-2. Methyl group in molecule Pr-1.6is derived from trimethylaluminum, which also works as Lewis acid in the process of decyanation. The structures of Pr-1.5 and Pr-1.6 were further confirmed by X-ray single crystal diffraction, exhibiting planar structures with strong π-π interaction. In addition, different substituents greatly influence the packing patterns of phthalorubines, while molecules Pr-1.5 pack as “head-tail” pattern and Pr-1.6as “head-head” pattern. We also studied the photophysical properties of these two new phthalorubines. Pr-1.5and Pr-1.6 exhibit similar absorption spectra to reported compounds but totally different emission efficiencies. It suggests electron donating groups is beneficial to high quantum yield. The facile synthetic method and properties reported in this work would greatly help the development of phthalorubines.

Key words: phthalorubines, fused rings, decyanation, dyes, heterocycles

引用此文

李凌燕, 郑玮, 李承辉. 无取代酞荭的高效制备及其新衍生物的研究[J]. 化学学报, 2021, 79(1): 81-86.

Ling-Yan Li, Wei Zheng, Cheng-Hui Li. A Facile Synthetic Method and New Derivatives of Phthalorubines[J]. Acta Chimica Sinica, 2021, 79(1): 81-86.

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图/表 7

图1. 利用Rh(I)催化剂制备Pr-2及本工作中利用Ni催化剂制备Pr-2

Figure 1. Preparation of Pr-2 using Rh(I) catalyst and the preparation of Pr-2 using Ni catalyst in this work

Entry ^a	Ni(acac) ₂/mmol	PCy ₃/mmol	AlMe ₃/mmol	(Me ₂SiH) ₂O/mmol	Toluene/mL	Yield ^b /%
1	0.3	0.9	3	1	1	13
2	0.6	1.8	6	2	1	30
3	1.2	3.6	20	4	1	10
4	1.2	3.6	20	4	4	26
5	1.2	3.6	10	4	4	58
6	1.2	3.6	10	-	4	19
7	1.2	3.6	-	4	4	-
8	1.2	3.6	-	-	4	-
9 ^c	1.2	3.6	10	4	4	43
10 ^d	1.2	3.6	10	4	4	48

表1. 反应物配比及溶剂用量对反应的影响

Table1. The influence of reactant ratio and solvent dosage in the reaction

Entry	Pr-1.5	Pr-1.6	Pr-2
1	4	10	13
2	7	17	30
3	4	9	10
4	15	23	26
5	3	10	58
6	2	26	19
7	0	0	0
8	0	0	0
9	21	12	35
10	3	26	33

表2. Pr-1.5, Pr-1.6及Pr-2在不同反应条件下的产率(%)

Table 2. The yield (%) of Pr-1.5, Pr-1.6 and Pr-2 under different reaction conditions

图2. Pr-1.5 (a)和Pr-1.6 (b)的1H NMR

Figure 2. 1H NMR of Pr-1.5 (a) and Pr-1.6 (b)

图3. Pr-1.5, Pr-1.6以及Pr-2的反应机理

Figure 3. Reaction mechanism of Pr-1.5, Pr-1.6 and Pr-2

图4. Pr-1.5和Pr-1.6的晶体结构

Figure 4. X-ray structures of Pr-1.5 and Pr-1.6

图5. (a)酞荭衍生物的紫外-可见吸收光谱以及在可见光下的照片和(b)荧光发射光谱以及在紫外光(365 nm)下的照片(拍摄照片所用浓度为10–4mol/L. 从左到右依次为Pr-1, Pr-1.5, Pr-1.6, Pr-2)

Figure 5. (a) Ultraviolet-visible absorption spectrum and photos under visible light, and (b) fluorescence emission spectrum and photos under ultraviolet light (365 nm) of phthalorubines derivatives. (Concentration for photos is 10–4 mol/L. From left to right: Pr-1, Pr-1.5, Pr-1.6, Pr-2)

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无取代酞荭的高效制备及其新衍生物的研究

A Facile Synthetic Method and New Derivatives of Phthalorubines

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