基于Aldol缩合反应的碳碳双键共价有机框架材料的设计合成

doi:10.16085/j.issn.1000-6613.2021-0025

摘要/Abstract

摘要：

具有C₃对称性的三甲基三嗪（TMT）分别与2,4,6-三(4-醛基苯基)-1,3,5-三嗪（TFPT）、均三苯甲醛（TFB）和四氟对苯二甲醛（TFBA）在酸或者碱催化条件下发生Aldol缩合反应，成功构建出3种新型的碳碳双键桥联的共价有机框架材料（TMT-TFPT-COF、TMT-TFB-COF、TMT-TFBA-COF）。本研究通过Material Studio、ZEO⁺⁺等软件对材料进行结构的精确解析，并结合粉末X射线衍射（PXRD）、傅里叶红外光谱（FTIR）等表征手段确定了材料的结构、连接方式及其荧光特性。结果表明，这3种较高结晶度的新型共价有机框架材料均为二维层层堆积结构，其中碱催化条件下合成的TMT-TFPT-COF、TMT-TFB-COF材料呈现出良好的荧光性质，此类荧光COFs材料在光催化、化学传感器等方面具有很好的应用潜力。

关键词: 共价有机框架材料, 多孔有机材料, 碳碳双键, Aldol反应

Abstract:

Three new olefin-linked covalent organic frameworks were successfully constructed via Aldol condensation by using 2,4,6-trimethyl-1,3,5-triazine (TMT) with C₃-symmetry and aromatic aldehydes as building units. Under hydrothermal conditions, TMT-TFPT-COF [with 2,4,6-tris(4-formylphenyl)-1,3,5-triazine (TFPT)] and TMT-TFB-COF [with benzene-1,3,5-tricarboxaldehyde (TFB)] were successfully synthesized using NaOH as catalyst, while TMT-TFBA-COF [with 2,3,5,6-tetrafluorobenzene-1,4-dicarbaldehyde (TFBA)] was constructed via trifluoroacetic acid (TFA) catalyst. The COFs structures and olefin-linkages were illustrated by theoretical modeling, FTIR and other characterization methods. The results indicated that all these COFs were constructed via two-dimensional eclipsed structure, and the fluorescent COFs (TMT-TFPT-COF and TMT-TFB-COF) would show great potential applications in the photocatalysis and chemical sensors.

Key words: covalent organic frameworks (COFs), porous organic materials, olefin linkage, Aldol condensation

中图分类号:

TB32

陈建松, 孙楠楠, 高强, 魏伟. 基于Aldol缩合反应的碳碳双键共价有机框架材料的设计合成[J]. 化工进展, 2021, 40(12): 6765-6776.

CHEN Jiansong, SUN Nannan, GAO Qiang, WEI Wei. Novel synthesis of olefin-linked covalent organic frameworks via aldol condensation[J]. Chemical Industry and Engineering Progress, 2021, 40(12): 6765-6776.

图/表 15

参考文献 27

1	DIERCKS C S, YAGHI O M. The atom, the molecule, and the covalent organic framework[J]. Science, 2017, 355(6328).
2	ZHOU H C, LONG J R, YAGHI O M. Introduction to metal-organic frameworks[J]. Chemical Reviews, 2012, 112(2): 673-674.
3	HAN X, YUAN C, HOU B, et al. Chiral covalent organic frameworks: design, synthesis and property[J]. Chemical Society Reviews, 2020, 49(17): 6248-6272.
4	LI W Q, HUANG X F, ZENG T W, et al. Thiazolo[5,4-d]thiazole-based donor-acceptor covalent organic frameworks for sunlight-driven hydrogen evolution[J]. Angewandte Chemie International Edition, 2021, 60(4): 1869-1874.
5	CÔTE A P, BENIN A I, OCKWIG N W, et al. Porous, crystalline, covalent organic frameworks[J]. Science, 2005, 310(5751): 1166-1170.
6	GENG K, HE T, LIU R Y, et al. Covalent organic frameworks: design, synthesis, and functions[J]. Chemical Reviews, 2020, 120(16): 8814-8933.
7	刘春晖, 马晓莉. 共价有机框架材料的最新进展[J]. 化工进展, 2019, 38(11): 4978-4900.
	LIU C H, MA X L. Latest development of covalent organic frameworks[J]. Chemcial Industry and Engineering Progress, 2019, 38(11): 4978-4990.
8	KANDAMBETH S, MALLICK A, LUKOSE B, et al. Construction of crystalline 2D covalent organic frameworks with remarkable chemical (acid/base) stability via a combined reversible and irreversible route[J]. Journal of the American Chemical Society, 2012, 134(48): 19524-19527.
9	LI X, ZHANG C L, CAI S L, et al. Facile transformation of imine covalent organic frameworks into ultrastable crystalline porous aromatic frameworks[J]. Nature Communications, 2018, 9(1): 2998-3006.
10	WEI P F, QI M Z, WANG Z P, et al. Benzoxazole-linked ultrastable covalent organic frameworks for photocatalysis[J]. Journal of the American Chemical Society, 2018, 140(13): 4623-4631.
11	XU H, GAO J, JIANG D L. Stable, crystalline, porous, covalent organic frameworks as a platform for chiral organocatalysts[J]. Nature Chemistry, 2015, 7(11): 905-912.
12	JIN E, ASADA M, XU Q, et al. Two-dimensional sp² carbon-conjugated covalent organic frameworks[J]. Science, 2017, 357(6352): 673-676.
13	BECKER D, BISWAL B P, KALENCZUK P, et al. Fully sp²-carbon-linked crystalline two-dimensional conjugated polymers: insight into 2D poly(phenylenecyanovinylene) formation and its optoelectronic properties[J]. Chemistry, 2019, 25(26): 6562-6568.
14	CHEN R F, SHI J L, MA Y, et al. Designed synthesis of a 2D porphyrin-based sp² carbon-conjugated covalent organic framework for heterogeneous photocatalysis[J]. Angewandte Chemie International Edition, 2019, 58(19): 6430-6434.
15	LENZ R W, HANDLOVITS C E. Thermally stable hydrocarbon polymers: polyterephthalylidenes[J]. The Journal of Organic Chemistry, 1960, 25(5): 813-817.
16	LYU H, DIERCKS C S, ZHU C, et al. Porous crystalline olefin-linked covalent organic frameworks[J]. Journal of the American Chemical Society, 2019, 141(17): 6848-6852.
17	WEI S, ZHANG F, ZHANG W B, et al. Semiconducting 2D triazine-cored covalent organic frameworks with unsubstituted olefin linkages[J]. Journal of the American Chemical Society, 2019, 141(36): 14272-14279.
18	BI S, YANG C, ZHANG W B, et al. Two-dimensional semiconducting covalent organic frameworks via condensation at arylmethyl carbon atoms[J]. Nature Communications, 2019, 10(1): 2467.
19	BI S, THIRUVENGADAM P, WEI S, et al. Vinylene-bridged 2D covalent organic frameworks via knoevenagel condensation of tricyanomesitylene[J]. Journal of the American Chemical Society, 2020, 142(27): 11893-11900.
20	FORSBERG J H, SPAZIANO V T, KLUMP S P, et al. Lanthanide(Ⅲ) ion catalyzed reaction of ammonia and nitriles: synthesis of 2,4,6-trisubstituted-s-triazines[J]. Journal of Heterocyclic Chemistry, 1988, 25(3): 767-770.
21	ACHARJYA A, PACHFULE P, ROESER J, et al. Vinylene-linked covalent organic frameworks by base-catalyzed aldol condensation[J]. Angewandte Chemie International Edition, 2019, 58(42): 14865-14870.
22	ACHARJYA A, LONGWORTH-DUNBAR L, ROESER J, et al. Synthesis of vinylene-linked covalent organic frameworks from acetonitrile: combining cyclotrimerization and aldol condensation in one pot[J]. Journal of the American Chemical Society, 2020, 142(33): 14033-14038.
23	刘伟. 共价有机框架材料的制备及其传感和催化性能研究[D]. 兰州: 兰州大学, 2019.
	LIU W. Preparation of covalent organic frameworks and studies on their senor and catalytic properties[D]. Lanzhou: Lanzhou University, 2019.
24	LIU H C, GU Y R, DAI Y X, et al. Pressure-induced blue-shifted and enhanced emission: a cooperative effect between aggregation-induced emission and energy-transfer suppression[J]. Journal of the American Chemical Society, 2020, 142(3): 1153-1158.
25	RAO K V, HALDAR R, MAJI T K, et al. Dynamic, conjugated microporous polymers: visible light harvesting via guest-responsive reversible swelling[J]. Physical Chemistry Chemical Physics, 2016, 18(1): 156-163.
26	ZHANG L, LI H J, HE H J, et al. Structural variation and switchable nonlinear optical behavior of metal-organic frameworks[J]. Small, 2021, 17(6): e2006649.
27	LI X, GAO Q, WANG J F, et al. Tuneable near white-emissive two-dimensional covalent organic frameworks[J]. Nature Communications, 2018, 9(1): 2335-2344.

原子	x/a	y/b	z/c	原子	x/a	y/b	z/c
H1	0.5632	0.1603	1.0	C10	-0.9990	-0.4846	1.0
H2	0.3991	0.2557	1.0	C11	-1.1656	-0.5350	1.0
C3	0.6006	0.3478	1.0	C12	-0.9625	-0.3323	1.0
C4	-0.6468	-0.4016	1.0	C13	-0.8738	-0.3083	1.0
C5	-0.8479	-0.3737	1.0	H14	-0.8285	-0.2386	1.0
N6	-0.7330	-0.4198	1.0	H15	-0.9049	-0.5180	1.0
C7	-1.0260	-0.4209	1.0	H16	-1.0438	-0.5552	1.0
C8	-1.1202	-0.4492	1.0	H17	-0.9813	-0.2821	1.0
C9	-0.9137	-0.4618	1.0	N18	0.6837	0.4159	1.0

原子	x/a	y/b	z/c	原子	x/a	y/b	z/c
H1	0.5632	0.1603	1.0	C10	-0.9990	-0.4846	1.0
H2	0.3991	0.2557	1.0	C11	-1.1656	-0.5350	1.0
C3	0.6006	0.3478	1.0	C12	-0.9625	-0.3323	1.0
C4	-0.6468	-0.4016	1.0	C13	-0.8738	-0.3083	1.0
C5	-0.8479	-0.3737	1.0	H14	-0.8285	-0.2386	1.0
N6	-0.7330	-0.4198	1.0	H15	-0.9049	-0.5180	1.0
C7	-1.0260	-0.4209	1.0	H16	-1.0438	-0.5552	1.0
C8	-1.1202	-0.4492	1.0	H17	-0.9813	-0.2821	1.0
C9	-0.9137	-0.4618	1.0	N18	0.6837	0.4159	1.0

原子	x/a	y/b	原子	x/a	y/b
H1	0.3549	0.3728	C5	0.3811	0.5779
H2	0.6382	0.6273	N6	0.4693	0.7143
C3	0.5634	0.5197	C7	0.6145	0.4228
C4	0.4306	0.4801	C8	0.5263	0.2814

原子	x/a	y/b	原子	x/a	y/b
H1	0.3549	0.3728	C5	0.3811	0.5779
H2	0.6382	0.6273	N6	0.4693	0.7143
C3	0.5634	0.5197	C7	0.6145	0.4228
C4	0.4306	0.4801	C8	0.5263	0.2814

原子	x/a	y/b	z/c	原子	x/a	y/b	z/c
N1	0.6895	0.4054	0.5	C7	0.7368	0.3813	0.5
C2	0.8556	0.4122	0.5	H8	0.8177	0.4809	0.5
C3	0.8058	0.4297	0.5	H9	0.8392	0.3595	0.5
C4	0.9292	0.4589	0.5	F10	0.9444	0.3636	0.5
C5	0.9596	0.5291	0.5	F11	1.0762	0.4393	0.5
C6	1.0291	0.5692	0.5