Aminal-Linked Covalent Organic Frameworks

doi:10.6023/cjoc202604053

Abstract

Covalent organic frameworks (COFs) are crystalline organic porous polymers with promising applications in many fields owing to their distinctive structures and properties. Linkages serve as critical targets for modulating their physicochemical performance and expanding application scopes. Aminal linkages possess tetrahedral configuration and favorable reaction reversibility, which have been merely confined to organic synthesis for a long period. Aminal-linked COFs were first reported in 2019, which filled the research gap in crystalline porous materials. Such materials display unique physicochemical properties and tremendous functional potentials. Nevertheless, current studies on aminal-linked COFs are extremely scarce. Their development progress fails to match their potential application value, owing to unique bond formation, high requirement for structural matching, and limited monomers. Accordingly, on the basis of topological classifications, this review systematically summarizes the structural characteristics, physicochemical properties and application fields of aminal-linked COFs. We further analyze the current research status and major bottlenecks, and prospect future research directions. This work is expected to provide references for structural design, performance optimization and application extension, and promote the further development of aminal-linked COFs.

Key words: covalent organic frameworks (COFs), aminal, linkage, tetrahedral configuration, topological structure

Cite this article

Zexin Gao, Zhenxue Wang, Wenzhuang Wang, Qiaoyan Qi, Rongran Liang, Xin Zhao. Aminal-Linked Covalent Organic Frameworks[J]. Chinese Journal of Organic Chemistry, 2026, 46(9): 3356-3371.

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Fig. & Tab. 15

Figure 1. Examples of linkages in COFs

Figure 2. Summary of reported aminal-linked COFs with different topologies

Figure 3. (a) Synthesis of Aminal-COF-1 and Aminal-COF-2; PXRD patterns and simulated crystal structures with different stacking modes of (b) Aminal-COF-1 and (c) Aminal-COF-2; N2 adsorption-desorption isotherms and pore size distribution profiles of (d) Aminal- COF-1 and (e) Aminal-COF-2 Copyright 2019, American Chemical Society.

Figure 6. (a) Absolute solid-state photoluminescence quantum yields of reported luminescent COFs and 2D conjugated polymers; (b) Design strategies for highly luminescent COFs Copyright 2024, American Chemical Society.

Figure 9. (a) Synthesis, (b) PXRD pattern, (c) N2 adsorption-desorption isotherm and pore size distribution profile, (d) simulated structure of PA-TA-COF; (e) Cycling performance of PA-TA-COF at 1.0 A•g－1 for 400 cycles; (f) Rate capabilities of PA-TA COF at various current densities Copyright 2021, Springer Nature.

Figure 11. (a) Synthesis and (b) N2 adsorption-desorption isotherm and pore size distribution profile of hcTPA-PZ COF; (c) Fabrication process and (d) separation performance of the hcTPA-PZ COF membrane Copyright 2026, American Chemical Society.

Figure 13. (a) Simplified Jablonski diagram for the sTTA upconversion process with triplet-triplet energy transfer (TTET) occurring between dissolved porphyrin and polymer suspension, exciton energy transfer (EET) within the polymer framework, and triplet-triplet annihilation (TTA) occurring between emitter units incorporated into the polymer framework; (b) Upconversion in solution driven by the diffusion of excited emitter molecules; (c) Upconversion in solid state driven by the EET between emitter units in the polymeric network Copyright 2026, Wiley-VCH.

COF		Topology	Interlayer distance/Å			BET surface area/(m²•g^－1)		Pore size/Å		Application	Reference
Aminal-COF-1		cpi	6.06			1169		5.2/8.2		Sensing	[31,56,57]
Aminal-COF-2		cpi	6.60			1168		5.4/8.2		—	[31]
DD-COF		cpi	6.06			805.98		5.4/7.5		Fluorescence	[58]
Por-Aminal-COF		cpi	3.96			813.04		6.3/13.9		Photocatalysis	[63]
TPTA-Pz-COF		cpi	7.45			1470		10		Electrocatalysis	[32]
PA-TA COF	p-hcb			6.20	—		7.3		Battery membrane separation			[54,71]
hcTPA-PZ COF	p-hcb			6.20	842		6.2		Gas separation			[72]
KUF-3	p-hcb			6.23	1268		7.3		Gas separation			[73]
Ant-COF-H	p-hcb			4.74	363		—		Energy conversion			[75]
Ant-COF-OH	p-hcb			4.96	256		—		Energy conversion			[75]
KUF-2	hxl-a			6.12	1169		3.9/5.9		Gas separation			[73]

Table 1. Summary of reported aminal-linked COFs

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