We successfully synthesized two new and exciting COFs, showcasing the versatility of COF design. For the convincing structural elucidation of 4A2E-PDA-COF TEM data was necessary to provide good evidence for the ABC stacking. The synthesized linker, which has not previously been reported, offers the unique advantage of forming larger pores compared to COFs based on the reported [1,1′-biphenyl]-3,3′,5,5′-tetracarbaldehyde with a similar structural motif. Those only form the kgm networks. In a 50 mL crimp vial, 2-bromoisophthalaldehyde (5.00 g, 23.5 mmol, 1.00 equiv.) and N-bromosuccinimide (5.00 g, 28.1 mmol, 1.20 equiv.) was dissolved in concentrated sulfuric acid (25 mL) and stirred at 85 °C for 16 h. The solution was poured into a solution of a stoichiometric amount of sodium bicarbonate in water and the product was extracted several times into dichloromethane (DCM). The solvent was removed under reduced pressure and the residue was purified by flash chromatography (CH/DCM; 1:1). The product was obtained as an off-white solid in a yield of 69% (4.76 g). In a 100 mL 3-neck flask, 2,5-dibromoisophthalaldehyde (1.00 g, 3.42 mmol, 1.25 equiv.) and (4methoxycarbonylphenyl)boronic acid (493 mg, 2.74 mmol, 1.00 equiv.) were dissolved in dry 1,4dioxane (15 mL) and bubbled for 20 min. Pd(dppf)Cl2 (100 mg, 137 µmol, 5 mol%) was added and the solution was bubbled for additional 10 min. K3PO4 (1.74 g, 8.22 mmol, 3.00 equiv.) was dissolved in water (5 mL) and degassed for 10 min. Afterwards it was added to the reaction mixture. The reaction was stirred at 90 °C for 16 h. After cooling to room temperature, the reaction mixture was filtered and the solvents were removed under reduced pressure. The precipitate was dissolved in DCM (40 mL) and washed with water (3 * 50 mL) and brine (1 * 50 mL). The organic phase was dried over Na2SO4 and evaporated under reduced pressure. The crude residue was purified via flash column chromatography (CH:EtOAc). A higher catalyst concentration leads to dehalogenation reaction. Yield: 599 mg (63%, 1.73 mmol) The substitution pattern was also verified via X-ray structure analysis of a single crystal grown by slow evaporation of CDCl3. The crystal structure has been deposited to the CCDC under the number: CCDC-2312146. Following a literature procedure , in a 50 mL crimp vial under a nitrogen atmosphere, 2,5-dibromo-p-xylene (1.06 g, 4.00 mmol, 1.00 equiv.), B2pin2 (3.05 g, 12.0 mmol, 3.00 equiv.), Pd(dppf)Cl2 (0.196 g, 0.24 mmol, 0.06 equiv.), and KOAc (2.36 g, 24.0 mmol, 6.00 equiv.) were dissolved in dry DMF(40 mL) and degassed with N2 for 20 min. The reaction mixture was heated at 85 °C for 48 h. The reaction mixture was cooled down to room temperature, then added to water before being extracted with DCM (50 mL). Combined organic layers were washed with water (2 * 100 mL) and brine (100 mL), then dried with Na2SO4 and evaporated under reduced pressure. The crude product was purified by recrystallization in MeOH. The product was obtained as a beige solid in a yield of 77% (1.11 g) In a 100 mL 3-neck flask under a nitrogen atmosphere, methyl 4'-bromo-2',6'-diformyl-[1,1'-biphenyl]-4-carboxylate (882 mg, 2.54 mmol, 2.50 equiv:), 1,4-Bis(pinacolatoboronyl)-2,5-dimethylbenzene (362 mg, 1.01 mmol, 1.00 equiv:) and Pd(PPh3)4 (133 mg, 115 μmol, 0.10 equiv) were dissolved in a mixture of dry toluene and dry 1,4-dioxane (1:1; 16 mL) and degassed with N2 for 15 min. K2CO3 (796 mg, 5.76 mmol, 5.00 equiv.), dissolved in water (4 mL), was degassed for 10 min and added to the reaction mixture. The reaction was heated to 110 °C for 16 h. After the reaction cooled down to room temperature, the insoluble precipitate was filtered off and washed with EtOAc and water and dissolved in DCM (White solid). To increase the yield, the organic phase of the reaction mixture was washed with water (2 * 20 mL). After phase separation, the aqueous phase was extracted with DCM (3* 20 mL). The combined organic extracts were dried over Na2SO4 and the solvent was removed under reduced pressure. The crude material was purified via column chromatography of silica gel with CH/DCM as an eluent.