A Facile Synthetic Method and New Derivatives of Phthalorubines

doi:10.6023/A20080389

Acta Chimica Sinica ›› 2021, Vol. 79 ›› Issue (1): 81-86.DOI: 10.6023/A20080389 Previous Articles Next Articles

Article

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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Abstract

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

Cite this article

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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Fig. & Tab. 7

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

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

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

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

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

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

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)

References 16

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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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