Structure Of Covalent Organic Frameworks Research Articles

Eco-Friendly High-Performance Symmetric All-COF/Graphene Aqueous Zinc-Ion Batteries.

Developing high-performance aqueous symmetric all-organic batteries (SAOBs) by replacing metal-based batteries or batteries with organic electrolytes is highly attractive to achieve a greener rechargeable world. However, such a new energy storage system still exhibits unsatisfactory rate capability and cycling stability due to the limitations in electrode materials screening. Here, a novel covalent organic framework (COF) containing abundant CN and CO for the electrode material is designed, which is combined with graphene and assembled into all-COF/graphene batteries for the first time. Moreover, the co-storage of Zn2+ and H+ in COF can be achieved in a mild aqueous electrolyte. Impressively, benefiting from the extended porous structure of COF, plentiful active reaction sites, more extensive electron delocalization from CO modification at molecular level, as well as enhanced fast H+ storage capacity of graphene and CO in COF, this kind of SAOBs show excellent cycle life and high rate performance (over 15000 cycles with a capacity of 80 mAh g-1 at a high current density of 5 A g-1 in pouch cell). This work will open a new window for the design of high-performance aqueous organic batteries, further moving toward a more eco-friendly electrochemical world.

Innovative COF@MXene composites for high performance energy applications

AbstractAs a new type of composite two-dimensional material formed by the combination of Covalent Organic Frameworks (COFs) and two- dimensional (2D) MXenes, COF/MXene heterostructures (COF@MXene) inherit the stable porous two-dimensional structure of COFs and the excellent electrochemical performance and catalytic activity of MXenes, thus attracting widespread attention. Additionally, COF@MXene possesses various elemental affinity sites, efficient ion channels, and the ability to append various functional groups, which endow them with tremendous potential in electrochemical energy storage, energy conversion, and catalysis. Currently, there is a lack of extensive literature discussing the utilization of COF@MXene. The quest for enhanced physicochemical attributes through tailored modifications and composite strategies for COF@MXene is still a noteworthy hurdle. Furthermore, discovering novel application contexts that can harness the exceptional capabilities of these materials presents a formidable task. This review initiates with an exploration of the primary methodologies for synthesizing COF and MXene composites. Subsequently, it outlines the diverse applications of COF and MXene in energy storage, energy conversion, and environmental conservation. Lastly, it discusses the primary obstacles and future trajectories within these domains.

Rapid preparation and mechanism investigation of covalent organic framework membranes by 3D printing based on electrostatic spraying

Covalent organic framework (COF) has great advantages in the field of membrane separation, but the efficient and convenient preparation of COF membranes is still a challenge. Herein, we propose a novel method with green solvent for the preparation of COF membranes based on electrostatic spraying, which can be successfully prepared within 10 min, forming the TpPa COF with a pore size of 1.8 nm. Molecular dynamics simulations demonstrate that electrostatic spraying enhances the reaction rate by lowering the energy barrier and increasing the movement of reacting monomers. Atomization of the solvent in electrostatic spraying causes the rapid volatilization of the solvent, resulting in supersaturation of the generated TpPa, precipitation and crystallization, and promotes the formation of TpPa COF structure. The optimal COF membrane for the separation of Congo red wastewater is prepared by adjusting the voltage, concentration, and spraying time, with selectivity of Na2SO4 for Congo Red attaining 118 and water permeance reaching 70.2 L m-2 h-1 bar-1. This work not only elaborates the membrane preparation mechanism in the electrostatic spraying process, but also greatly shortens the time of COF membrane preparation compared to the traditional method (2–3 days), which contributes to the possibility for practical application of COF membranes.

Analyte-Induced Specific Regulation of Light-Responsive COF-Cu Nanozyme Activity for Ultrafast Thiram Colorimetric Sensing.

A light-responsive covalent-organic framework (COF) nanozyme, which integrates the advantages of the COF structure and light-stimulated nanozyme catalysis, is a class of sensing star materials with wide application prospects. However, the sensing methods based on light-responsive COF nanozymes are relatively single at present. Therefore, it is necessary to develop new sensing strategies to broaden its application in chemical sensing and achieve highly efficient detection. Here, a Cu2+-modified COF composite material (TpDA-Cu) was rationally designed. The addition of Cu significantly inhibits the excellent light-responsive nanozyme activity of TpDA itself. However, because of the restoration of the enzyme activity by thiram (Tr) and the oxidase mimic activity of the newly formed Cu/Tr complex, TpDA-Cu/Tr exhibits stronger light-responsive nanozyme activity. Enzyme kinetic data show that compared with TpDA, TpDA-Cu/Tr has a larger Vmax value, which can achieve efficient catalytic oxidation of 3,3',5,5'-tetramethylbenzidine (TMB). In addition, the strong coordination effect of Tr and TpDA-Cu also plays a key role in achieving ultrafast, sensitive, and selective colorimetric detection of Tr. This work develops a dual activity regulation strategy of light-responsive COF nanozymes based on analyte induction and provides a new perspective for the application of light-responsive COF nanozymes in the field of sensing.

Engineering designed functional covalent organic frameworks via pore surface modifications for effectively reducing the dielectric constant of polyimide-based electronic packaging materials

Polyimide (PI) is considered one of the most promising candidate materials for the microelectronics and wireless communication industries. Nevertheless, the relatively high dielectric constant of PI has become a significant obstacle, constraining its utilization in the realm of microelectronics. Herein, novel PI nanocomposite films were fabricated by incorporating covalent organic frameworks (COFs) and their functionalized counterparts (COF@POSS and COF@DTF) through post-synthetic modification. Among all PI nanocomposites films, PI/COF@POSS nanocomposite film including 2 wt% COF@POSS achieved the lowest dielectric constant (2.41) and dielectric loss (0.0076). These values represented a reduction of 22.5 % and 24 % compared to pure PI, respectively. The decrease in dielectric constant is ascribed to the combined influence of the porous structure of COF and the augmentation in free volume fraction caused by the steric hindrance of POSS. Additionally, the tensile strength of the PI/COF@POSS and PI/COF@DTF nanocomposite films increased up to 121.1 MPa and 112.0 MPa, representing a 95 % and 80 % improvement over pure PI, respectively. Furthermore, the introduction of COFs functionalized with POSS and DTF significantly enhanced the hydrophobicity of PI nanocomposite films. The combination of porous organic nanofillers with surface functionalization offers a feasible route to create low-k PI nanocomposite films with improved mechanical properties and hydrophobicity.

Engineering cell membrane-camouflaged COF-based nanosatellite for enhanced tumor-targeted photothermal chemoimmunotherapy

Dendritic cells (DCs) activation is crucial for regulating the antitumor immune response. However, the tumor's immunosuppressive environment significantly impedes antigen presentation and DCs maturation, thereby limiting the effectiveness of cancer immunotherapy. To address this challenge, we developed tumor cell membrane-coated covalent organic framework (COF) nanoparticles, loaded with mannose-modified gold nanoparticles and doxorubicin (Dox). This created a cell membrane-camouflaged COF-based nanosatellite designed to enhance tumor-targeted chemoimmunotherapy. The nanosatellite exhibits distinct photothermal properties and releases Dox in a pH-sensitive manner, targeting tumor cells to induce immunogenic cell death (ICD) and expose a wealth of antigens. Crucially, the COF structure is selectively degraded to release mannose-modified gold nanoparticles in the acidic environment. These nanoparticles capture antigens from the ICD and efficiently transport them to lymph nodes rich in DCs, facilitated by mannose receptor mediation. As a result, antigens are effectively presented to DCs, activating the immune response, significantly hindering tumor growth and lung metastasis in mice, and extending survival. This study pioneered innovative nano-preparations aimed at enhancing tumor immunotherapy.

Cell membrane-inspired COF/AAO hybrid nanofluidic membrane with ion current rectification properties for ultrasensitive detection of E. coli

Nanofluidic membranes hold great prospects in sensitive and rapid detection of bioanalysts, while remaining lacking robust and general approaches for specificity. In this work, we introduce a cell membrane-inspired nanofluidic membrane with excellent ion current rectification properties as a simple and robust platform for label-free and ultrasensitive biosensing. The asymmetric nanofluidic membrane is prepared by coupling a two-dimensional covalent organic framework (COF) membrane to an anodic aluminum oxide (AAO) nanochannel via hydrogen bonding. The prepared COF/AAO membrane presents selective ion transport due to the asymmetric structure and anion selectivity of COF. With the large surface area and abundant functional modification sites of COF, further grafting of the recognition unit can be easily achieved to mimic the recognition process of receptors and ligands on cell membranes. As a proof of concept, the application in bacterial detection is demonstrated by covalently bonded Concanavalin A as recognition units. The highly amplified ionic current based on ion current rectification properties of the COF/AAO membrane allows sensitive and selective bioanalysis. Specifically, the proposed asymmetric nanofluidic membrane presents a linear detection range from 10 to 106 CFU/mL with an ultralow detection limit of 7 CFU/mL for E. coli. This work reveals the great potential of COF/AAO hybrid nanofluidic membrane as a sensor for rapid and precise bioanalysis.

Tuning interlayer stacking of 2D covalent organic frameworks for high-resolution separation of C8 aromatic isomers

Covalent organic frameworks (COFs) has shown great potential as stationary phase in gas chromatography separation. However, designing COF stationary phases with high separation performance remains challenging. Here, we report a novel strategy to enhance the separation ability of COF stationary phases through tuning the interlayer stacking of COF. A rare interlayer modulation of 2D COFs from eclipsed-AA to slipped-AA was achieved through a two-step synthesis method. Simply changing the solvent used in step 1 allowed an interlayer modulation from slipped-AA to eclipsed-AA. As the proof-of-concept, 5,10,15,20-tetrakis(4-aminophenyl)-21H,23H-porphyrin (Tph) and 2,5-dihydroxyterephthalaldehyde (DHTA) were condensed to prepare 2D COF Tph-DHTA. The interlayer stacking of the 2D COF Tph-DHTA was tuned from eclipsed-AA model to slipped-AA by changing the solvent from o-dichlorobenzene + n-butanol (3:1, v/v) to tetrahydrofuran + n-butanol (1:7, v/v) in step 1. The as-prepared Tph-DHTA with slipped-AA stacking (s-Tph-DHTA) showed higher resolution and faster separation of C8 aromatic isomers than that with eclipsed-AA stacking (e-Tph-DHTA). The formation of slipping stacking of s-Tph-DHTA facilitated the thermodynamics, but did not affect the mass transfer resistance for the separation of C8 aromatic isomers. This work not only provides a promising way to modulate the stacking structure of COFs, but also opens a new strategy to design COF stationary phases for the separation of intractable isomers.

Electrostatically Designing Materials and Interfaces.

Collective electrostatic effects arise from the superposition of electrostatic potentials of periodically arranged (di)polar entities and are known to crucially impact the electronic structures of hybrid interfaces. Here, it is discussed, how they can be used outside the beaten paths of materials design for realizing systems with advanced and sometimes unprecedented properties. The versatility of the approach is demonstrated by applying electrostatic design not only to metal-organic interfaces and adsorbed (complex) monolayers, but also to inter-layer interfaces in van der Waals heterostructures, to polar metal-organic frameworks (MOFs), and to the cylindrical pores of covalent organic frameworks (COFs). The presented design ideas are straightforward to simulate and especially for metal-organic interfaces also their experimental implementation has been amply demonstrated. For van der Waals heterostructures, the needed building blocks are available, while the required assembly approaches are just being developed. Conversely, for MOFs the necessary growth techniques exist, but more work on advanced linker molecules is required. Finally, COF structures exist that contain pores decorated with polar groups, but the electrostatic impact of these groups has been largely ignored so far. All this suggest that the dawn of the age of electrostatic design is currently experienced with potential breakthroughs lying ahead.

Building Li–S batteries with enhanced temperature adaptability via a redox-active COF-based barrier-trapping electrocatalyst

Covalent organic frameworks (COFs) are promising materials for mitigating polysulfide shuttling in lithium-sulfur (Li–S) batteries, but enhancing their ability to convert polysulfides across a wide temperature range remains a challenge. Herein, we introduce a redox-active COF (RaCOF) that functions as both a physical barrier and a kinetic enhancer to improve the temperature adaptability of Li–S batteries. The RaCOF constructed from redox-active anthraquinone units accelerates polysulfide conversion kinetics through reversible C=O/C-OLi transformations within a voltage range of 1.7 to 2.8 V (vs. Li+/Li), optimizing sulfur redox reactions in ether-based electrolytes. Unlike conventional COFs, RaCOF provides bidentate trapping of polysulfides, increasing binding energy and facilitating more effective polysulfide management. In-situ XRD and ToF-SIMS analyses confirm that RaCOF enhances polysulfide adsorption and promotes the transformation of lithium sulfide (Li2S), leading to better sulfur cathode reutilization. Consequently, RaCOF-modified Li–S batteries demonstrate low self-discharge (4.0% decay over a 7-day rest), excellent wide-temperature performance (stable from −10 to +60 °C), and high-rate cycling stability (94% capacity retention over 500 cycles at 5.0 C). This work offers valuable insights for designing COF structures aimed at achieving temperature-adaptive performance in rechargeable batteries.

Nano-structured urchin-like photothermal covalent organic frameworks for efficient Solar-Driven interfacial water evaporation

Solar-driven interfacial water evaporation is a promising sustainable technology to alleviate the global energy crisis and clean water shortage. The design of advanced photothermal materials play the critical role to utilize photothermal heat for water evaporation. Covalent organic frameworks (COFs) as a new class of crystalline porous polymer semiconductor materials have been deemed as an ideal nanoscale platform for designing photothermal materials with notable features like highly ordered structures, porous open channels, and tunable structure and functionality. In this work, we focus on the regulation of the multi-scale structure of COFs and design hierarchically nano-structured photothermal COFs for efficient solar-driven interfacial water evaporation. At the molecular scale, we synthesize a photothermal functionalized COF-366-OH using photosensitive 5,10,15,20-tetrakis(4-aminophenyl) porphyrin (TAPP) and 2,5-dihydroxyterephthalaldehyde (DHTA) as building blocks. At the micro-nano scale, we introduce the π-conjugated catechol molecule 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) to regulate COF polycondensation and assembly, which enable the shaping of COF-366-OH into urchin-like nano-morphologies (namely UCOF-366-OH). The synthesized UCOF-366-OH exhibits high crystallinity, large surface area, excellent photothermal conversion capacity, and strong hydrophilicity. Furthermore, UCOF-366-OH is processed into a photothermal composite membrane. With localized solar heating and optimized water transport at the water evaporation interface, a high evaporation rate of 2.51 kg m−2h−1 with solar-to-vapor efficiency of 97.3 % is achieved. This work paves a new way for the multi-scale structural design of COF-based photothermal materials and highlights their innovative application in solar water evaporation.

Chiral microporous organic network/covalent organic framework/silica composites: Powerful and versatile chromatographic separation materials

Nowadays, covalent organic framework (COF) has shown great potential in chromatographic separation, and enriching the design of novel COF based stationary phases and broadening their application prospects remains of great significance. Microporous organic network (MON) is a novel type of porous material with large specific surface area and excellent stability connected by covalent bonding, which is extremely similar to COF. Especially, nano-sized MON has the characteristics of easy binding with silica matrix and superior chromatographic separation performance. In this work, the combination of MON and COF as the surface modification materials of silica gel was first explored. The conjugated network structure of MON and COF can improve the permeability of silica stationary phase, and the presence of abundant functional groups in COF and MON can enhance the separation ability for a series of aromatic compounds. Moreover, hydrophilic L-cysteine containing thiol group was cleverly introduced into MON/COF@SiO2via thiol-ene/yne click reactions to balance the hydrophilicity and hydrophobicity of stationary phase. The L-cysteine modified chiral MON/COF@SiO2 (CMON/CCOF@SiO2) was used for effective separation of various chiral/hydrophilic/hydrophobic analytes, and the CMON/CCOF@SiO2 was observed to exhibit superior separation ability to the CCOF@SiO2. Multi-mode chromatographic separation mechanisms were explored, demonstrating that multiple interactions were involved in the separation process. Finally, the CMON/CCOF@SiO2 was applied to detect the environmental endocrine disruptors in the water sample and pyridoxine in the tablet sample, respectively, indicating a great potential for application in actual sample detection.

Four-State Electrochromism in Tris(4-aminophenyl)amine- terephthalaldehyde-based Covalent Organic Framework.

Covalent organic frameworks (COFs) are of massive interest due to their potential application spanning diverse fields such as gas storage and separation, catalysis, drug delivery systems, sensing, and organic electronics. In view of their application-oriented quest, the field of electrochromism marked a significant stride with the reporting of the first electrochromic COF in 2019 [J. Am. Chem. Soc. 2019, 141, 19831-19838]. Since then, new and novel COF structures with electrochromic features (denoted as ecCOFs) have been searched continuously. Yet, only a handful of ecCOFs have been constructed to date. A closer look at these reports suggests that multielectrochromism (showing at least three redox color states) in a COF assembly has only been achieved once, manifested through three-state electrochromism [Angew. Chem. 2021, 133, 12606-1261]. Herein, we report four-state electrochromism in tris(4-aminophenyl)amine-terephthalaldehyde (TAPA-PDA)-based COF constructed through the metal-catalyst free Schiff base approach. The four-state (orange, pear, green, and cyan) electrochromism demonstrated by the TAPA-PDA ecCOF opens several futuristic avenues for ecCOF's end use in flip-flop logic gates, intelligent windows, decorative displays, and energy-saving devices.

Aggregation Induced Emission-Based Covalent Organic Frameworks for High-Performance Optical Wireless Communication.

Here, we report the first utilization of covalent organic frameworks (COFs) in optical wireless communication (OWC) applications. In the solid form, aggregation-induced emission (AIE) luminogen often shows promising emissive characteristics that augment radiative decays and improve fluorescence. We have synthesized an AIE-COF through the Knoevenagel condensation reaction by taking advantage of the ability to carefully design and alter the COF structure by integrating an AIE luminogen with linear building blocks. The synthesized AIE-COF exhibited a high solid-state photoluminescence quantum yield (∼39%) and a short photoluminescence lifetime (∼1 ns), crucial for achieving modulation bandwidth for high-speed OWC applications. For comparison, we constructed an aggregation-caused quenching based COF, showing a similar lifetime but almost insignificant quantum yield. The orthogonal frequency-division multiplexing modulation strategy employed by the AIE-COF demonstrates remarkable high-rate data transmission, with a wide -3 dB modulation bandwidth of nearly 200 MHz and achieving high net data rates of 825 Mb/s, outperforming traditional materials. These results open new avenues for the ability to design and finetune new COF materials for their utilization as color converters in developing cutting-edge OWC components, enabling faster and more efficient data transfer.

High-performance COFs composite nanofiltration membrane fabricated by organobase catalyst

Covalent Organic Frameworks (COFs) composite nanofiltration (NF) membrane has high permeation flux and rejection. However, the reaction rate of COFs is relatively slow. Adding acid catalyst is a common method to shorten reaction time. However, the dissatisfactory synthesis rate will lead to irregular structure of COFs materials. In this work, it is the first time to use organobase as a catalyst to prepare COFs composite membrane. The COFs structure will be optimized and the membrane performance can be enhanced. The prepared TpPa-PIP membrane compared with acid catalyzed TpPa-HAc membrane has better permeability, permeance of 89 L m−2·h−1·bar−1 and CR rejection of 99.54 %. This improvement is because of the TpPa-PIP intermediate made slower reaction speed that improves the overall regularity and crystallinity of COFs. Therefore, it is better method for broadening the application of organobase-catalyzed in preparing membranes.

Harnessing the clean energy: Phosphorus-alkynyl covalent organic frameworks for photocatalytic hydrogen production

Given the diminishing reserves of fossil fuels, the development of renewable alternative energy sources is of global importance. Photocatalytic hydrogen (H2) evolution stands out as a promising and cost-effective method to harness sunlight for producing carbon-free H2 fuel. Recently, two-dimensional (2D) covalent organic frameworks (COFs) have garnered considerable research interest in photocatalysis on account of their exceptional surface area and predictable assembly of diverse molecules with adjustable electronic properties. Herein, six 2D COFs are constructed by topologically assembling phosphorus-alkynyl functional moieties and benzene-based building units, including benzene (COF-1), triazine (COF-2), heptazine (COF-3), triphenyl-benzene (COF-4), triphenyl-triazine (COF-5), and triphenyl-heptazine (COF-6), employing first-principles calculations. Our computational results illustrate that the variation of benzene-based building units significantly regulates the electronic structures of COFs, all of which possess semiconductor properties with tunable bandgaps spanning from 1.56 to 2.56 eV. Of particular importance, COF-1, COF-2, COF-4, COF-5, and COF-6 can spontaneously stimulate the hydrogen evolution reaction (HER) under their own light-induced bias without the need for sacrificial agents and co-catalysts. Among them, COF-4 and COF-5 show the best HER activity without light-induced bias, with ΔG values of 0.02 and −0.01 eV, respectively, whose excellent photocatalytic performance can be ascribed to their appropriate electronic band structures, pronounced optical absorption, and low work functions. This finding offers profound insights for exploring other highly efficient HER photocatalysts.

Boosting photocatalytic multi-VOCs decontamination over COF-based heterojunction via targeted construction of Ov–M–N charge channel (M = Ti, Zn, W, Ce) and –NH2 functionalization

Covalent organic frameworks (COF) based materials have exhibited excellent gas and visible light absorption capability, yet are very difficult to generate strong oxidative species for photocatalytic mineralization of volatile organic compounds (VOCs). Here, a facile in situ modulation protocol developed could enable the growth of MOx (M = Ti, Zn, W, Ce) with oxygen vacancy (Ov) on –NH2-functionalized COF surfaces to construct NH2–COF/Ov–MOx Z–scheme heterojunctions of excellent stability and efficiency (98.3 %) in photo-oxidation of formaldehyde, acetaldehyde, and acetone. The –NH2 functionalization enhanced VOC chemisorption via H-bond interaction. Moreover, the constructed fast charge transfer channel (Ov–M–N) at the interface not only promoted directional migration of photo-excited carrier, activated adsorbed O2 and H2O to quickly generate strong •OH, but also effectively inhibited injurant formation to realize the precise control of the conversion path. These findings offer new insights into customizing the interfacial structure of COF for indoor air purification.

Cyclic Multi‐Site Chelation for Efficient and Stable Inverted Perovskite Solar Cells

Trap‐assisted non‐radiative recombination losses and moisture‐induced degradation significantly impede the development of highly efficient and stable inverted (p‐i‐n) perovskite solar cells (PSCs), which require high‐quality perovskite bulk. In this research, we mitigate these challenges by integrating thermally stable perovskite layers with Lewis base covalent organic frameworks (COFs). The ordered pore structure and surface binding groups of COFs facilitate cyclic, multi‐site chelation with undercoordinated lead ions, enhancing the perovskite quality across both its bulk and grain boundaries. This process not only reduces defects but also promotes improved energy alignment through n‐type doping at the surface. The inclusion of COF dopants in p‐i‐n devices achieves power conversion efficiencies (PCEs) of 25.64% (certified 24.94%) for a 0.0748‐cm2 device and 23.49% for a 1‐cm2 device. Remarkably, these devices retain 81% of their initial PCE after 978 hours of accelerated aging at 85˚C, demonstrating remarkable durability. Additionally, COF‐doped devices demonstrate excellent stability under illumination and in moist conditions, even without encapsulation.

Additive Mixing of Emissive Ligands in Covalent Organic Frameworks for White Light Emission.

Emissive covalent organic frameworks (COFs) are a promising class of crystalline materials that have demonstrated applications for sensing and light-emitting diodes. However, white light emission from a single COF has not been achieved yet as it requires multicomponent organic chromophores that simultaneously emit blue, green, and red light. In this work, we report the successful synthesis of a single COF with efficient white light emission by utilizing tunable emission properties of 2,1,3-benzothiadazole after incorporating different functional groups on its core structure, which results in the formation of three ligands, i.e., 4',4-(benzothiadiazole-4,7-diyl)-dibenzaldehyde (BTD), 4,4'-(benzoselenadiazole-4,7-diyl)-dibenzaldehyde (BSD), and 4,4'-(naphtho[2,3-c][1,2,3] selenadiazole-4,9-diyl)-dibenzaldehyde (NSD), that emit in the blue, green, and red regions of the visible light spectrum. We show that white light emission can only occur when BTD, BSD, and NSD are assembled in a single COF structure due to the facilitated energy transfer process from BTD to BSD/NSD. This work demonstrates a unique approach to developing new white light-emitting materials based on the COF structure.

Enhancing structural control in covalent organic frameworks through steric interaction-driven linker design.

Covalent Organic Frameworks (COFs) exhibiting kagome (kgm) structures are promising crystalline porous materials with two distinct pores. However, there are no reliable synthetic methods to exclusively target the kgm over the polymorphic square-lattice (sql) structure. To address this, we introduce a linker design strategy featuring bulky functional groups, which through steric interactions can hinder the sql net formation, thereby leading to a kgm structure. By rigid attachment of the methyl benzoate groups to a tetradentate COF linker, steric interactions with neighbouring linkers depending on the pore size become possible. The steric interaction was tuned by varying the complementary bidentate linear linker lengths, where the shorter phenylenediamine linker leads to steric hindrance and the formation of the kgm lattice, while with the longer benzidine linker, steric interaction is reduced leading to the sql lattice. Thus, control over the net can be exerted through steric interaction strengths. Additionally, structural analysis revealed the formation of the kgm COF with an unusual ABC stacking, leading to pearl string type pores instead of two distinct pore sizes. This COF system shows that steric interaction-driven design enhances control over COF structures, expanding the design toolbox, but also provides valuable insights into network formation and polymorphism.