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This work shows that hydroboration can be efficiently applied to the postsynthetic modification (PSM) of the Sonogashira-Hagihara coupling-based microporous organic polymers (MOPs). Hollow MOPs (H-MOPs) were prepared by template synthesis through the Sonogashira-Hagihara coupling of tetra(4-ethynylphenyl)methane with 1,4-diiodobenzene. The H-MOPs were used as platforms in the PSM-based functionalization. The heat-treatment of H-MOPs in the presence of a neat pinacolborane reagent resulted in the successful addition of pinacolborane groups to the internal alkynes of H-MOPs, generating H-MOPs with pinacolboranes (H-MOP-BPs). The pinacolborane moieties in the H-MOP-BP were further converted to boronic acid groups. The resultant H-MOP-BAs were used as heterogeneous organocatalysts in the CO

Synthetic methods and benefits of morphology-engineered microporous organic polymers (ME-MOPs) were reviewed.

Copper(I) oxide nanocubes were wrapped with an extremely uniform organic layer grown by self-controlled, Cu-mediated catalysis. This layer aided in retaining the initial cubic structure of the copper nanocubes during their use as a CO

A sustainable CO2 polymerization using surface activated zinc glutarate catalysts produces industrially useful polymers with good catalytic activity.

We suggest that 1,3-diynes are main reaction sites in the thiol–yne click-based main chain post-synthetic modification of conjugated microporous polymers.

The hydrogen evolution efficiency of MOP-based photocatalysts was enhanced with the aid of afterglow phosphorescent materials.

The development of a biomass-based polymer platform has become increasingly important to address environmental problems. In the present study, we present a furan-based polymer platform, furandiacyl...

The design and synthesis of phthalimide derivatives are important goals for applications in fields such as pharmaceutical science and optoelectronics. In the present study, a facile and convenient synthetic pathway (no heat or acid/catalyst needed) is devised to produce phthalimides from a biomass-derived furan by directly introducing an N-carbamate group at the C-2 position of the furan ring via thermal Curtius rearrangement. The electron-donating N-carbamate group increases the energy level of the highest occupied molecular orbital of the furan diene, resulting in a significant increase of the rate of the Diels-Alder reaction with maleimide compared to the conventional furfuryl furan. Interestingly, the Diels-Alder adduct smoothly undergoes aromatization (dehydration) to generate the phthalimide motif. It is shown that the biomass-derived phthalimides can produce supramolecular gels and act as sensors of basic anions like F

This work shows that the hydrogen evolution performance of conjugated microporous polymer (CMP)-based photocatalysts can be enhanced through their hollow shape engineering. Using a hollow microporous organic polymer (H-MOP) as a template, hollow Stille coupling-based CMP photocatalysts with Pd nanoparticles (H-MOP@SCMP-Pds) were prepared, showing enhanced hydrogen evolution rates up to 7100 μmol h−1 g−1 and apparent quantum yields up to 3.72% (@420 nm).

Conjugated microporous polymers (CMPs) have significant potential as electrode materials for electric energy storage devices due to their high surface areas, conjugation features, and chemical stability. However, low conductivity has limited their electrochemical performance. To realize the maximum capability of CMPs, a synthetic strategy for enhancing their conductivity is required. This work shows that during the synthesis of CMPs, carbon black (CB) nanoparticles can be entrapped in situ. Moreover, redox-active benzoquinone (BQ) species could be generated at the CMP to form CMP-BQ through post-synthetic modification. The resultant CB@CMP-BQs with the entrapped CB nanoparticles showed enhanced electrochemical performance as electrode materials for pseudocapacitors, compared with CMP-BQ. They showed capacitances up to 424 and 373 F g−1 at current densities of 0.5 and 1 A g−1, respectively. In addition, the optimal CB@CMP-BQ3 showed excellent cycling performance for 10 000 cycles.

This work introduces, for the first time, the energy harvesting performance of conjugated microporous polymers (CMPs) as tribo-positive materials for triboelectric nanogenerators (TENGs). Various nano or submicron CMP particles (CMP-X) were prepared by the Sonogashira coupling of 1,3,5-triethynylbenzene with 1,4-diiodoarenes. Optimized CMP-X nanoparticles in a polyurethane (PU) matrix showed excellent triboelectrification performance, displaying peak-to-peak voltages of up to 411 V and a maximum power density of 0.80 mW cm−2. Moreover, an optimized 5.0% CMP-H@PU-based TENG could be utilized as a power source for the charging of an electrolytic capacitor and for the operation of 100 LEDs.

A microporous organic polymer (MOP) was utilized for the engineering of nanoparticulate CeO2 in a hollow carbon matrix (H-C/CeO2). After CeO2 nanoparticles were incorporated into a hollow MOP platform (H-MOP) through the decomposition of cerium acetate, successive carbonization produced H-C/CeO2. The redox feature of defective CeO2 in a conductive carbon matrix induced promising pseudocapacitive behavior. In particular, the H-C/CeO2 showed excellent electrochemical performance in an alkaline electrolyte (KOH), due to the hydroxide ion-assisted redox behavior of defective CeO2. H-C/CeO2-3 with an optimized amount of CeO2 showed specific capacitances of up to 527 (@0.5 A g−1) and 493 F g−1 (@1 A g−1). Even at high current densities of 10 and 20 A g−1, the H-C/CeO2-3 maintained high capacitances of 458 and 440 F g−1, respectively. After 10 000 cycling tests, the H-C/CeO2-3 retained the 94–95% capacitance of the first cycle.

The reactor fouling is a notorious obstacle in managing continuous synthetic processes of polyketones. The fouling raises synthetic costs and reduces the bulk density of polymers. Thus, efficient seed materials are required for antifouling performance. Hollow microporous organic polymers (HMOPs) were prepared using ZIF-8 nanoparticles as templating materials. Sulfonic groups were incorporated into HMOP via a post synthetic approach. The resultant HMOP–SO3H (20–90 μg/mL in methanol) showed successful catalyst activation and antifouling performance in polyketone synthesis.

Microporous organic polymer nanoparticles bearing tetraphenylethylene moieties (MOPTs) were prepared in the presence of poly(vinylpyrrolidone) (PVP). The PVP was entrapped into the microporous network of MOPT to form MOPT-P and played the roles of size control, porosity enhancement, and surface property management. MOPT materials without PVP showed superhydrophobicity with a water contact angle of 151°. In comparison, the MOPT-P showed excellent water compatibility. Moreover, due to the aggregation-induced emission property of tetraphenylethylene moieties, the MOPT-P showed emission and excellent emission-based sensing of nitrophenols in water with Ksv values in the range of 1.26 × 104 ∼ 3.37 × 104 M–1. It is noteworthy that the MOPT-P used water only as a sensing medium and did not require additional organic solvents to enhance water dispersibility of materials. The MOPT-P could be recovered and reused for the sensing at least five times.

Hollow microporous organic networks were prepared by using silica spheres as the template and tris(4-ethynylphenyl)amine and 2,6-diiodo-9,10-anthraquinone as the building blocks for the Sonogashira coupling. The resultant materials bearing triphenylamine and anthraquinone moieties showed efficient visible light absorption and catalytic activities in the photochemical oxidative coupling of benzylamines. Through the comparison studies of hollow and nonhollow catalytic materials, the diffusion pathway effect of the substrates was clearly observed in the photochemical conversion of benzylamines.

Conjugated microporous polymer (CMP)-based energy-storage materials were developed for pseudocapacitors. Nanoparticulate CMP (N-CMP) with an average diameter of 41±4 nm was prepared through kinetic growth control in the Sonogashira coupling of 1,3,5-triethynylbenzene with 1,4-diiodobenzene. The N-CMP is rich in a diphenylacetylene moiety in its chemical structure. Through the FeCl3 -catalyzed oxidation of diphenylacetylene moieties, N-CMP with benzil moieties (N-CMP-BZ) was prepared and showed enhanced electrochemical performance as an electrode material of pseudocapacitors, compared with CMP, CMP-BZ, and N-CMP. In model studies, the benzil was redox active and showed two-electron reduction behavior. The excellent electrochemical performance of N-CMP-BZ is attributable to the enhanced utilization of functional sites by a nanosize effect and the additional redox contribution of benzil moieties.

This work introduces a so called “caffeine method” for morphology evolution of microporous organic polymer (MOP). In a proper reaction medium such as triethylamine, caffeine undergoes dynamic self-...

Multifunctional drug delivery systems were designed and engineered by template synthesis of a microporous organic polymer (MOP) and by postsynthetic modification. Hollow MOP spheres bearing Fe3O4 yolks (Fe3O4@Void@MOP) were prepared by the synthesis of MOP on Fe3O4@SiO2 nanoparticles and by successive silica etching. In addition to the magneto-thermal function of Fe3O4 yolks, an aggregation-induced emission (AIE) feature was incorporated into the Fe3O4@Void@MOP through a homocoupling of tetra(4-ethynylphenyl)ethylene to form Fe3O4@Void@MOP-TE. Folate groups were further introduced into Fe3O4@Void@MOP-TE through the postsynthetic modification based on the thiol-yne click reaction. The resultant Fe3O4@Void@MOP-TE-FA showed multifunctionality in antitumoral therapy via folate receptor targeting, doxorubicin delivery, AIE-based imaging, and the magneto-thermal feature.

Flexible and metal-economical electromagnetic interference (EMI) shielding films were fabricated based on microporous organic polymer (MOP) chemistry. MOP with amino groups (MOP-A) could be introduced to the surface of poly(ethylene terephthalate) (PET) fibers. Due to the microporosity and amino groups of MOP-A, Ag+ could be easily incorporated into PET@MOP-A. Through Ag-catalyzed electroless Cu deposition, PET@MOP-A@Cu films were fabricated. The morphological and chemical structures of the PET@MOP-A@Cu were characterized by scanning electron microscopy, X-ray diffraction studies, and X-ray photoelectron spectroscopy. Among the films, the PET@MOP-A@Cu-40 with 41 wt % Cu (a thickness of 0.64 μm) showed excellent EMI shielding performance with 64.3-73.8 dB against an EM of 8-12 GHz. Moreover, it showed retention of the original EMI shielding performance against 1000 bending (R = 5 mm) tests.

Stille coupling was applied to synthesize microporous organic polymers (MOPs). Metallic Pd was in situ self-supported during the networking of 1,3,6,8-tetrabromopyrene with 1,4-bis(tributylstannyl)benzene to form Stille coupling-based MOP (St-MOP)@Pd. The size of St-MOP particles and the amount of metallic Pd in St-MOP@Pd depended on the amount of Pd catalyst. As the amount of Pd catalyst increased, the size of St-MOP particles decreased with an increase of metallic Pd, due to the increased St-MOP nuclei in the early growth stage of St-MOP. The St-MOP bearing pyrenes showed absorption and emission of visible light and St-MOP@Pd showed excellent catalytic performance in the visible light-driven Suzuki–Miyaura coupling. The optimal St-MOP@Pd-2 (0.14 mol% Pd) showed a TON of 657 and a TOF of 219 h−1 in the visible light-driven Suzuki–Miyaura coupling of 1-acetyl-4-bromobenzene and phenylboronic acid at 25 °C. The optimal amount of St-MOP and metallic Pd in St-MOP@Pd was critical to achieve excellent catalytic performance. The overall photocatalytic principles of St-MOP@Pd were rationalized by computational simulation.

This work shows a new post-synthetic strategy of a microporous organic polymer (MOP) based on AB2 polymerization chemistry (polymerization of AB2-type monomers). Hollow MOP (H-MOP) platforms were prepared by template synthesis via Sonogashira coupling of 1,4-dibromo-2,5-diethynylbenzene. The amount of terminal alkynes in the H-MOP was amplified via AB2 polymerization. Through the thiol–yne click reaction, aliphatic sulfonic acids were incorporated into the terminal alkyne-enriched H-MOP. The resultant solid acid catalysts showed efficient performance in the synthesis of soluble cellulose derivatives.

A microporous organic polymer (MOP) was utilized for the engineering of nanoparticulate CeO

This work shows that a hollow and microporous metal-free N,N'-phenylenebis(salicylideneimine) (salphen) network (H-MSN) can be engineered by Sonogashira coupling of [tetraiodo{di(Zn-salphen)}] building blocks with 1,4-diethynylbenzene in the presence of silica templates and by successive Zn and silica etching. Iron(III) ions could be incorporated into the H-MSN to form hollow and microporous Fe-disalphen networks (H-MFeSN) with enhanced microporosity and surface area. The H-MFeSN showed efficient catalytic performance and recyclability in the CO2 conversion to cyclic carbonates.

The so-called colloidal template synthesis has been applied to the preparation of surface-engineered nanoadsorbents. Colloidal microporous organic network nanotemplates (C-MONs), which showed a high surface area (611 m2 g-1 ) and enhanced microporosity, were prepared through the networking of organic building blocks in the presence of poly(vinylpyrrolidone) (PVP). Owing to entrapment of the PVP in networks, the C-MONs showed good colloidal dispersion in EtOH. MoS2 precursors were incorporated into the C-MONs and heat treatment afforded core-shell-type C@MoS2 nanoparticles with a diameter of 80 nm, a negative zeta potential (-39.5 mV), a high surface area (508 m2 g-1 ), and excellent adsorption performance towards cationic dyes (qmax =343.6 and 421.9 mg g-1 for methylene blue and rhodamine B, respectively).

This work shows that the shape-controlled microporous organic polymer (MOP) can be utilized for the morphological engineering of another class of MOP materials. The morphology of a hyper-cross-linked polymer (HCP) was successfully engineered on the hollow conjugated microporous polymer (CMP). Through the postsynthetic modification of HCP bearing BINOLs (HCP-B) on the hollow CMP-like material (H-CMPL), the HCP bearing BINOL phosphoric acid (HCP-BP) was engineered on the H-CMPL platform. The resultant H-CMPL@HCP-BP showed good catalytic performance as a heterogeneous catalytic system and excellent recyclability in the ring-opening polymerization of ε-caprolactones to poly(caprolactone).

Gel electrolytes were synthesized by the formation of microporous organic polymers in the presence of 0.077–0.77 M LiClO4 and N-methylpyrrolidone. Electrochromic devices fabricated using the gel electrolytes showed enhanced operation stability, compared with those fabricated using liquid electrolytes, which is attributable to the efficient separation of working viologens from counting molecules.

This work unravels the unified mechanistic principle of the tubular shape evolution of microporous organic polymers (MOPs) prepared by the Sonogashira coupling of ethynylarenes and haloarenes. Using ionic building blocks (self-templates), in situ generated salts (in situ templates), or salt additives (additive templates), tubular MOP materials could be engineered. The assembled ionic species can act as morphology templates in the covalent assembly of building blocks to form MOP tubes.

This work shows that microporous organic network (MON) chemistry can be applied to the dual photodynamic and chemical therapy of cancer cells. Water-compatible and Zn-phthalocyanine (ZnPhT) loaded MON nanoparticles were engineered through size-controlled synthesis using poly(vinylpyrrolidone) (PVP) as a surfactant, followed by postsynthetic sulfonation of materials. The ZnPhT was successfully loaded on the sulfonated MON nanoparticles (N-SMONs) via coulombic interaction between anionic sulfonate and cationic ZnPhT. Because of their microporosity and high surface area, DOX was loaded efficiently on the ZnPhT/N-SMON nanoparticles. The resultant DOX/ZnPhT/N-SMON showed synergistic performance in the dual photodynamic and chemotherapy of cancer cells and tumors in in vitro and in vivo tests.

This work shows that hollow microporous organic polymer (H-MOP-A) with activated internal alkynes as IR probes can be prepared by template synthesis based on acyl Sonogashira-Hagihara coupling at room temperature. The H-MOP-A is a versatile platform in the main chain PSM based on nonradical thiol-yne click reaction. Moreover, an IR peak of internal alkynes in the H-MOP-A is very intense and could be utilized in the monitoring of thiol-yne click-based main chain PSM. The functionalized H-MOP-A with carboxylic acids (H-MOP-CA) showed efficient adsorption toward Ag + ions. The resultant H-MOP-CA-Ag showed excellent performance in the CO 2 fixation to α-alkylidene cyclic compounds.