Design and Synthesis of Bisulfone-Linked Two-Dimensional Conjugated Microporous Polymers for CO2 Adsorption and Energy Storage

We have successfully synthesized two types of two-dimensional conjugated microporous polymers (CMPs), Py-BSU and TBN-BSU CMPs, by using the Sonogashira cross-coupling reaction of BSU-Br2 (2,8-Dibromothianthrene-5,5′,10,10′-Tetraoxide) with Py-T (1,3,6,8-Tetraethynylpyrene) and TBN-T (2,7,10,15-Tetraethynyldibenzo[g,p]chrysene), respectively. We characterized the chemical structure, morphology, physical properties, and potential applications of these materials using various analytical instruments. Both Py-BSU and TBN-BSU CMPs showed high thermal stability with thermal decomposition temperatures (Td10) up to 371 °C and char yields close to 48 wt%, as determined by thermogravimetric analysis (TGA). TBN-BSU CMPs exhibited a higher specific surface area and porosity of 391 m2 g−1 and 0.30 cm3 g−1, respectively, due to their large micropore and mesopore structure. These CMPs with extended π-conjugated frameworks and high surface areas are promising organic electroactive materials that can be used as electrode materials for supercapacitors (SCs) and gas adsorption. Our experimental results demonstrated that the TBN-BSU CMP electrode had better electrochemical characteristics with a longer discharge time course and a specific capacitance of 70 F g−1. Additionally, the electrode exhibited an excellent capacitance retention rate of 99.9% in the 2000-cycle stability test. The CO2 uptake capacity of TBN-BSU CMP and Py-BSU CMP were 1.60 and 1.45 mmol g−1, respectively, at 298 K and 1 bar. These results indicate that the BSU-based CMPs synthesized in this study have potential applications in electrical testing and CO2 capture.


Introduction
While digital life brings comfort, it also presents difficulties that people must consider. This energy source and storage support the advent of electronic products, and the energy relies primarily on the supply of the natural environment [1][2][3][4][5][6][7]. Renewable energy sources include solar and wind power, ocean energy, hydropower, and biomass; limited energy sources come from industrial fossil fuels such as coal, natural gas, and oil [8][9][10][11][12][13][14][15]. The pursuit of green environmental protection without affecting the life experience of most consumers, or how to ensure the supply and demand of energy while improving economic effects, is a heavy part of technology today. An increasingly well-known energy storage device to deal with this situation is the supercapacitor (SC), which has been studied since the 19th century [16][17][18][19][20][21][22][23][24][25]. SCs were developed for the same purpose as secondary batteries and conventional capacitors. They are all used for the convenience of energy storage, but supercapacitors have fewer limitations and wider prospects than the other two [26][27][28][29][30].

Synthesis and Characterization of Synthesized Monomers, Py-BSU and TBN-BSU CMPs
The BSU-Br2 monomer was prepared in two steps. The THT molecule was brominated in a neat Br2 solution in AcOH to afford THT-Br2 as a white solid (Scheme S1). THT-Br2 was then reacted with H2O2 solution in AcOH solution at 90 °C to produce BSU-Br2 as a white solid (Scheme S2). The FTIR pattern of BSU-Br2 ( Figure S4) showed peaks at 3064 cm −1 for the aromatic rings and 1171 cm −1 for the SO2 group, indicating the successful formation of BSU-Br2 from THT-Br2. Furthermore, the 1 H and 13 C NMR data confirmed the chemical structure of BSU-Br2 ( Figures S5 and S6). The FTIR and NMR results for other synthesized monomers in this study, such as THT-Br2, Py-Br4, Py-TMS, Py-T, TPE, TPE-Br4, TBN-Br4, and TBN-TMS, have been provided and discussed in detail in the experimental section (Figures S1-S3 and S7-S25). The signals at 3279, 3065, 2186, and 1618 cm −1 are attributed to the absorption characteristics for ≡C-H, aromatic C-H, C≡C, and C=C stretching in the Py-T structure ( Figure S11). The 1 H NMR pattern ( Figure S12) of Py-T peaked at 8. 68, 8.38, and 3.67 ppm, corresponding to the phenyl and alkynyl groups, respectively. In addition, the aromatic carbon resonances appeared in the range 133. 80-127.80, 84.50, and 82.00 ppm in the 13 C NMR spectrum ( Figure S13) of Py-T due to the presence of aromatic and alkynyl units. As shown in Schemes S5-S7, there were three steps during the preparation of the TBN-T monomer. In dry nitromethane and DCM, TPE-Br4 was reacted with anhydrous FeCl3 to produce a yellow powder of TBN-Br4. To prepare TBN-TMSA, a TBN-Br4 precursor was combined with (trimethylsilyl)acetylene (TMSA) in the presence of CuI with diethylamine as the solvent. The treatment of TBN-TMSA with K2CO3 in methanol and DCM to produce a yellow solid allowed for the effective synthesis of TBN-T. The peaks in the FTIR spectrum of TBN-T ( Figure S26) at 3291, 3057, 2106, and 1604 cm −1 were attributed to C≡C-H, aromatic C-H, C≡C, and C=C stretching, respectively. The proton signal was observed in the 1 H NMR spectra of TBN-T ( Figure S27

Synthesis and Characterization of Synthesized Monomers, Py-BSU and TBN-BSU CMPs
The BSU-Br 2 monomer was prepared in two steps. The THT molecule was brominated in a neat Br 2 solution in AcOH to afford THT-Br 2 as a white solid (Scheme S1). THT-Br 2 was then reacted with H 2 O 2 solution in AcOH solution at 90 • C to produce BSU-Br 2 as a white solid (Scheme S2). The FTIR pattern of BSU-Br 2 ( Figure S4) showed peaks at 3064 cm −1 for the aromatic rings and 1171 cm −1 for the SO 2 group, indicating the successful formation of BSU-Br 2 from THT-Br 2 . Furthermore, the 1 H and 13 C NMR data confirmed the chemical structure of BSU-Br 2 ( Figures S5 and S6). The FTIR and NMR results for other synthesized monomers in this study, such as THT-Br 2 , Py-Br 4 , Py-TMS, Py-T, TPE, TPE-Br 4 , TBN-Br 4 , and TBN-TMS, have been provided and discussed in detail in the experimental section (Figures S1-S3 and S7-S25). The signals at 3279, 3065, 2186, and 1618 cm −1 are attributed to the absorption characteristics for ≡C-H, aromatic C-H, C≡C, and C=C stretching in the Py-T structure ( Figure S11). The 1 H NMR pattern ( Figure S12) of Py-T peaked at 8.68, 8.38, and 3.67 ppm, corresponding to the phenyl and alkynyl groups, respectively. In addition, the aromatic carbon resonances appeared in the range 133. 80-127.80, 84.50, and 82.00 ppm in the 13 C NMR spectrum ( Figure S13) of Py-T due to the presence of aromatic and alkynyl units. As shown in Schemes S5-S7, there were three steps during the preparation of the TBN-T monomer. In dry nitromethane and DCM, TPE-Br 4 was reacted with anhydrous FeCl 3 to produce a yellow powder of TBN-Br 4 . To prepare TBN-TMSA, a TBN-Br 4 precursor was combined with (trimethylsilyl)acetylene (TMSA) in the presence of CuI with diethylamine as the solvent. The treatment of TBN-TMSA with K 2 CO 3 in methanol and DCM to produce a yellow solid allowed for the effective synthesis of TBN-T. The peaks in the FTIR spectrum of TBN-T ( Figure S26) at 3291, 3057, 2106, and 1604 cm −1 were attributed to C≡C-H, aromatic C-H, C≡C, and C=C stretching, respectively. The proton signal was observed in the 1 H NMR spectra of TBN-T ( Figure S27) at 3.30 ppm for C≡C-H. In addition, the presence of aromatic rings and C≡C units in the TBN-T compound caused carbon peaks at 135.70-101.60, 84.21, and 78.87 ppm, as seen in the 13 C-NMR spectrum ( Figure S28).
As shown in Scheme 1, Py-BSU CMP (Scheme 1a) and TBN-BSU CMP (Scheme 1b) were prepared by reacting BSU-Br 2 with Py-T and TBN-T in a mixture of DMF/Et 3 N for 3 days to afford dark red powder for Py-BSU CMP and yellow solid for TBN-BSU CMP. The solubility test in different organic solvents (NMP, DMSO, DMF, MeOH, EtOH, DCM, and THF) revealed the insolubility of these materials compared to their corresponding monomers (BSU-Br 2 , Py-T, and TBN-T) and confirmed that both BSU-CMP frameworks had a high cross-linking density. The chemical characteristics of Py-BSU and TBN-BSU CMPs were identified by Fourier transform infrared spectroscopy and solid-state 13 C nuclear magnetic resonance spectroscopy (ssNMR). A schematic of the corresponding structure is shown in Figure 1a [75][76][77]. The above results confirmed that Py-BSU CMP and TBN-BSU CMP were successfully constructed through a coupling reaction. In addition, the thermogravimetric analysis (TGA) in Figure 1d and Table 1 demonstrates the good thermal stability of the BSU-CMP materials under a nitrogen atmosphere, which is due to the high degree of cross-linking of the BSU-CMP materials after the Sonogashira cross-coupling reaction. The 5% weight loss (T d5 ) of Py-BSU CMP and TBN-BSU CMP occurred at 320 and 338 • C, 10% weight loss (T d10 ) of Py-BSU CMP and TBN-BSU CMP occurred at 383 and 386 • C, respectively, and the char yields at 800 • C were 48 and 56 wt%, respectively.  Figure S28). As shown in Scheme 1, Py-BSU CMP (Scheme 1a) and TBN-BSU CMP (Scheme 1b) were prepared by reacting BSU-Br2 with Py-T and TBN-T in a mixture of DMF/Et3N for 3 days to afford dark red powder for Py-BSU CMP and yellow solid for TBN-BSU CMP. The solubility test in different organic solvents (NMP, DMSO, DMF, MeOH, EtOH, DCM, and THF) revealed the insolubility of these materials compared to their corresponding monomers (BSU-Br2, Py-T, and TBN-T) and confirmed that both BSU-CMP frameworks had a high cross-linking density. The chemical characteristics of Py-BSU and TBN-BSU CMPs were identified by Fourier transform infrared spectroscopy and solid-state 13 C nuclear magnetic resonance spectroscopy (ssNMR). A schematic of the corresponding structure is shown in Figure 1a [75][76][77]. The above results confirmed that Py-BSU CMP and TBN-BSU CMP were successfully constructed through a coupling reaction. In addition, the thermogravimetric analysis (TGA) in Figure 1d and Table 1 demonstrates the good thermal stability of the BSU-CMP materials under a nitrogen atmosphere, which is due to the high degree of cross-linking of the BSU-CMP materials after the Sonogashira cross-coupling reaction. The 5% weight loss (Td5) of Py-BSU CMP and TBN-BSU CMP occurred at 320 and 338 °C, 10% weight loss (Td10) of Py-BSU CMP and TBN-BSU CMP occurred at 383 and 386 °C, respectively, and the char yields at 800 °C were 48 and 56 wt%, respectively.   The porosity behavior of Py-BSU CMP and TBN-BSU CMP was determined using the Brunauer-Emmett-Teller (BET) theory, and the specific surface area and pore characteristics were confirmed through nitrogen adsorption/desorption analysis at 77 K. Both Py-BSU CMP and TBN-BSU CMP were vacuum degassed at 150 • C for 8 h to eliminate the huge effect caused by water and other gases in the gas adsorption experiment. According to the IUPAC classification, the Py-BSU CMP in Figure 2a exhibits a type V isotherm with H 2 hysteresis loops that reflect typical ink bottle holes with uneven pore size distributions or close-packed interstitial pores of spherical particles. While TBN-BSU CMP in Figure 2b exhibits a type I isotherm with an H 1 hysteresis loop, the surge in the region of low relative pressure (<0.02) confirms that this material has a large number of micropores. The specific surface areas of Py-BSU CMP and TBN-BSU CMP were 42 and 391 m 2 g −1 . Their corresponding total pore volumes are 0.07 and 0.30 cm 3 g −1 , respectively. In addition, we estimated the pore size distribution (PSD) of Py-BSU CMP and TBN-BSU CMP from the N 2 adsorption isotherm using the nonlocal density functional theory (NLDFT). The results show that the average pore diameters of Py-BSU CMP ( Figure 2c) and TBN-BSU CMP ( Figure 2d)  The porosity behavior of Py-BSU CMP and TBN-BSU CMP was determined using the Brunauer-Emmett-Teller (BET) theory, and the specific surface area and pore characteristics were confirmed through nitrogen adsorption/desorption analysis at 77 K. Both Py-BSU CMP and TBN-BSU CMP were vacuum degassed at 150 °C for 8 h to eliminate the huge effect caused by water and other gases in the gas adsorption experiment. According to the IUPAC classification, the Py-BSU CMP in Figure 2a exhibits a type V isotherm with H2 hysteresis loops that reflect typical ink bottle holes with uneven pore size distributions or close-packed interstitial pores of spherical particles. While TBN-BSU CMP in Figure 2b exhibits a type I isotherm with an H1 hysteresis loop, the surge in the region of low relative pressure (<0.02) confirms that this material has a large number of micropores. The specific surface areas of Py-BSU CMP and TBN-BSU CMP were 42 and 391 m 2 g −1 .
Their corresponding total pore volumes are 0.07 and 0.30 cm 3 g −1 , respectively. In addition, we estimated the pore size distribution (PSD) of Py-BSU CMP and TBN-BSU CMP from the N2 adsorption isotherm using the nonlocal density functional theory ( The spatial ordering of Py-BSU CMP and TBN-BSU CMP was determined by X-ray diffraction analysis in the angular (2θ) range of 5-50°. Crystalline peaks were not observed The spatial ordering of Py-BSU CMP and TBN-BSU CMP was determined by X-ray diffraction analysis in the angular (2θ) range of 5-50 • . Crystalline peaks were not observed in the XRD results, and the broad peaks in Figure S29 show the amorphous features of Py-BSU CMP and TBN-BSU CMP. The powder morphologies by SEM images of Py-BSU CMP and TBN-BSU CMP are shown in Figure 3a,b, respectively. The former nanosheets agglomerated slightly; the latter cluster phenomenon occurs because of the extremely small size of spherical nanoparticles. Furthermore, the presence of carbon (C), oxygen (O), and sulfur (S) atoms in both Py-BSU CMP and TBN-BSU CMP were confirmed through EDS-SEM mapping (Figure 3c-i). The weight contents of C, O, and S in Py-BSU CMP were 78.80, 16.82, and 4.38%, respectively ( Figure S30a). In TBN-BSU CMP, the weight contents were 70.9, 26.64, and 2.46% for C, O, and S atoms, respectively ( Figure S30b). The TEM images ( Figure S31) of both Py-BSU CMP and TBN-BSU CMP show that the structure was amorphous and that nanometer-scale holes were distributed uniformly. and TBN-BSU CMP are shown in Figure 3a,b, respectively. The former nanosheets ag-glomerated slightly; the latter cluster phenomenon occurs because of the extremely small size of spherical nanoparticles. Furthermore, the presence of carbon (C), oxygen (O), and sulfur (S) atoms in both Py-BSU CMP and TBN-BSU CMP were confirmed through EDS-SEM mapping (Figure 3c-i). The weight contents of C, O, and S in Py-BSU CMP were 78.80, 16.82, and 4.38%, respectively ( Figure S30a). In TBN-BSU CMP, the weight contents were 70.9, 26.64, and 2.46% for C, O, and S atoms, respectively ( Figure S30b). The TEM images ( Figure S31) of both Py-BSU CMP and TBN-BSU CMP show that the structure was amorphous and that nanometer-scale holes were distributed uniformly. The CO2 capacities of TBN-BSU CMP and Py-BSU CMP were 1.6 and 1.45 mmol g −1 , respectively, as displayed in Figure 4. The excellent performance of TBN-BSU CMP for CO2 uptake is due to its high pore volume, BET surface area, and tunable pore size. The CO 2 capacities of TBN-BSU CMP and Py-BSU CMP were 1.6 and 1.45 mmol g −1 , respectively, as displayed in Figure 4. The excellent performance of TBN-BSU CMP for CO 2 uptake is due to its high pore volume, BET surface area, and tunable pore size.

Electrochemical Measurements of Py-BSU CMP and TBN-BSU CMP
We used 1 M KOH aqueous solution as the electrolyte in a three-electrode system and compared the electrochemical performance of Py-BSU CMP and TBN-BSU CMP by cyclic voltammetry (CV) and galvanostatic charge-discharge (GCD). The working electrode, counter electrode, and reference electrode of the three-electrode system are composed of glassy carbon, platinum, and Hg/HgO, respectively. The CV curves of Py-BSU CMP and TBN-BSU CMP at scan rates from 5 to 200 mV s −1 are shown in Figure 5a,b, and the overall leaf-like shape suggests a response originating from the electric double-layer capacitance (EDLC). Among them, as the scan rate increased from 5 to 200 mV s −1 , the maintained shape of the CV curves indicates the excellent rate capability of the material. Figure 5c,d report the GCD curves detected at current densities ranging from 0.5 to 20 A g −1 . Slightly curved triangles are characteristic of EDLC.

Electrochemical Measurements of Py-BSU CMP and TBN-BSU CMP
We used 1 M KOH aqueous solution as the electrolyte in a three-electrode system and compared the electrochemical performance of Py-BSU CMP and TBN-BSU CMP by cyclic voltammetry (CV) and galvanostatic charge-discharge (GCD). The working electrode, counter electrode, and reference electrode of the three-electrode system are composed of glassy carbon, platinum, and Hg/HgO, respectively. The CV curves of Py-BSU CMP and TBN-BSU CMP at scan rates from 5 to 200 mV s −1 are shown in Figure 5a,b, and the overall leaf-like shape suggests a response originating from the electric double-layer capacitance (EDLC). Among them, as the scan rate increased from 5 to 200 mV s −1 , the maintained shape of the CV curves indicates the excellent rate capability of the material. Figure 5c,d report the GCD curves detected at current densities ranging from 0.5 to 20 A g −1 . Slightly curved triangles are characteristic of EDLC.

A g -1 1 A g -1 2 A g -1 3 A g -1 5 A g -1 7 A g -1 10 A g -1 15 A g -1 20 A g -1
(c) (d) As shown in Figure 6a, at a current density of 0.5 A g −1 , the specific capacitance values of Py-BSU CMP and TBN-BSU CMP calculated by GCD curves were 38 and 70 F g −1 . In contrast, TBN-BSU CMP exhibited superior electrochemical behavior due to the more extended conjugated structure of the TBN unit and high surface area. The improvement of the π system increased the charge transfer efficiency in contact with the electrolyte and further promoted the performance of the supercapacitor through this process. From another point of view, the capacitance value shrunk when the current density increased from 0.5 to 20 A g −1 . This can be attributed to the diffusion problem caused by electrolyte ions not fully permeating into the electrode material due to insufficient time in the high current environment. Figure 6b,c demonstrate the measured stability over 2000 cycles at a current density of 10 A g −1 . The capacitance retention rates of Py-BSU CMP and TBN-BSU CMP were 99.8% and 99.9%, respectively. The extremely small capacitance decay indicates that the material has excellent electrochemical reversibility. Figure 6d shows that the specific capacitance value of TBN-BSU CMP precursor (70 F g −1 ) is higher than CoPc-CMP (13.  As shown in Figure 6a, at a current density of 0.5 A g −1 , the specific capacitance values of Py-BSU CMP and TBN-BSU CMP calculated by GCD curves were 38 and 70 F g −1 . In contrast, TBN-BSU CMP exhibited superior electrochemical behavior due to the more extended conjugated structure of the TBN unit and high surface area. The improvement of the π system increased the charge transfer efficiency in contact with the electrolyte and further promoted the performance of the supercapacitor through this process. From another point of view, the capacitance value shrunk when the current density increased from 0.5 to 20 A g −1 . This can be attributed to the diffusion problem caused by electrolyte ions not fully permeating into the electrode material due to insufficient time in the high current environment. Figure 6b,c demonstrate the measured stability over 2000 cycles at a current density of 10 A g −1 . The capacitance retention rates of Py-BSU CMP and TBN-BSU CMP were 99.8% and 99.9%, respectively. The extremely small capacitance decay indicates that the material has excellent electrochemical reversibility. Figure 6d shows that the specific capacitance value of TBN-BSU CMP precursor (70 F g −1 ) is higher than CoPc-CMP In Figures 7 and S32, the EIS results indicated that Py-BSU CMP and TBN-BSU CMP have slightly different Nyquist curves, suggesting they have different resistances. In detail, TBN and Py-BSU CMP showed a specific resistance of 9 and 23 ohm, respectively. The charge transfer rate studies were tested through EIS within the frequency range of 100 mHz to 100 kHz at the open circuit potential and 5 mV as an amplitude. It should be noticed that a smaller semi-circuit was observed for TBN-BSU CMP with lower resistance than Py-BSU CMP, indicating a lower resistance and lower charge transfer resistance. The results were fitted to a simulation circuit composed of four elements of the series resistance (Rs), the charge-transfer resistance (Rct), the electrical double-layer capacitance (Cdl), and the Warburg diffusion impedance (Wd), as displayed in the inset of the figure of Randles Cell. It is important to notice that low-resistance materials can improve energy storage because they have fast charge transport capabilities. Therefore, TBN-BSU CMP is a better choice for energy storage applications. Due to its high surface area, structural integrity, and compatibility with bis-sulfone units, TBN-BSU CMP exhibited this behavior [83][84][85][86][87][88]. In Figures 7 and S32, the EIS results indicated that Py-BSU CMP and TBN-BSU CMP have slightly different Nyquist curves, suggesting they have different resistances. In detail, TBN and Py-BSU CMP showed a specific resistance of 9 and 23 ohm, respectively. The charge transfer rate studies were tested through EIS within the frequency range of 100 mHz to 100 kHz at the open circuit potential and 5 mV as an amplitude. It should be noticed that a smaller semi-circuit was observed for TBN-BSU CMP with lower resistance than Py-BSU CMP, indicating a lower resistance and lower charge transfer resistance. The results were fitted to a simulation circuit composed of four elements of the series resistance (R s ), the charge-transfer resistance (R ct ), the electrical double-layer capacitance (C dl ), and the Warburg diffusion impedance (W d ), as displayed in the inset of the figure of Randles Cell. It is important to notice that low-resistance materials can improve energy storage because they have fast charge transport capabilities. Therefore, TBN-BSU CMP is a better choice for energy storage applications. Due to its high surface area, structural integrity, and compatibility with bis-sulfone units, TBN-BSU CMP exhibited this behavior [83][84][85][86][87][88].

Synthesis of 2,8-Dibromothianthrene (THT-Br 2 )
Br 2 solution (6 mL, 0.116 mol) was added dropwise to thianthrene (3.24 g, 0.015 mol) dissolved in AcOH (60 mL). The reactant was heated to 90 • C and agitated for one day. Distilled water (30 mL) was then added to the mixture once it had cooled to room temperature. The resultant precipitate was filtered out and properly washed with a 5% NaHCO 3 solution and water. The further purification by recrystallization from MeOH/DCM afforded THT-Br 2 a white solid (Scheme S1). FTIR ( Figure S1 H 2 O 2 (70 mL, 2.984 mol) was added dropwise to THT-Br 2 (2.55 g, 0.007 mol), dissolved in glacial acetic acid (55 mL). The reactant was heated to 90 • C and stirred for 1 day. After cooling to room temperature, the resulting precipitate was filtered off and washed thoroughly with 5% NaHCO 3 solution and H 2 O. Finally, the BSU-Br 2 product was purified by recrystallization from MeOH/DCM mixture affording BSU-Br 2 a white solid (Scheme S2). FTIR ( Figure S4 Br 2 (3.5 mL, 0.068 mol) was injected dropwise into a Py monomer (3.00 g, 0.015 mol) dissolved in nitrobenzene (30 mL). The reaction mixture was then heated to 120 • C and stirred for 24 h. After filtration through EtOH, the green solid was collected and dried at 60 • C (Scheme S3). FTIR ( Figure S7): 3053 and 682 (C-Br group) cm −1 .

Synthesis of 2,7,10,15-Tetrakis(trimethylsilyl)ethynyl)dibenzo[g,p]chrysene (TBN-TMS)
In 125 mL of diethylamine, 1.5 g of TBN-Br 4 (2.33 mmol) was dissolved. Then the solution was treated with a combination of CuI (0.11 g), PdCl 2 (PPh 3 ) 2 (0.08 g), and ethynyltrimethylsilane (1.83 g, 18.63 mmol). After 24 h of stirring at 80 • C, the solvent was removed under reduced pressure, and the product was then purified using flash chromatography on a silica gel column with DCM as an eluent to produce a yellow solid (Scheme S6, 1.3 g, 86%). FTIR ( Figure S23 The TBN-TMS (1 g, 1.40 mmol) was dissolved in 60 mL of MeOH and 40 mL of DCM before being mixed for 24 h with 1.2 g of K 2 CO 3 (8.65 mmol). Following this, the solvent was removed using a vacuum. The resulting solid was dissolved with 50 mL of DCM and then extracted with H 2 O to afford TBN-T (0.8 g, 80%) as an orange solid after the solvent was removed under vacuum (Scheme S7). FTIR (KBr, cm −1 , Figure S26

Conclusions
In this study, we successfully synthesized two conjugated microporous polymers, Py-BSU CMP and TBN-BSU CMP, using Sonogashira-Hagihara cross-coupling of BSU-Br 2 with Py-T and TBN-T, respectively. We characterized the chemical structures, physical properties, porosity, and morphology of these CMPs using various analytical techniques, including FTIR, solid-state 13 C NMR spectroscopy, BET, SEM, and TEM. Both Py-BSU CMP and TBN-BSU CMP showed excellent thermal stability with T d10 up to 383 • C and char yield up to 48 wt% at 800 • C as measured by TGA. We also investigated the electrochemical performance of these CMPs and found that TBN-BSU CMP exhibited better performance due to its more extended π-conjugated system, higher specific surface area (391 m 2 g −1 ), and total pore volume (0.30 cm 3 g −1 ). Under the three-electrode measurement system, TBN-BSU CMP showed significantly better electrochemical performance with a capacitance of 70 F g −1 at a current density of 0.5 A g −1 compared to Py-BSU CMP. TBN-BSU CMP also demonstrated excellent stability with less capacitance decay (99.9%) in long-life-cycle energy storage devices. Finally, we believe that these BSU-linked CMPs, Py-BSU and TBN-BSU CMPs, hold great potential for other applications such as H 2 production and gas conversion. Overall, our findings suggest that these CMPs could be attractive candidates for various energy storage and conversion applications.  Figure S22. 13 C-NMR spectrum of TBN-Br 4 . Figure S23. FTIR spectrum of TBN-TMS; Figure S24

Data Availability Statement:
The data presented in this study are available on request from the corresponding author.