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Comprehensive Summary: Advanced functionalization‐decorated porous organic polymers (POPs) are emerging as a prominent research focus, spanning from their construction to applications in gas storage and separation, catalysis, energy storage, electrochemistry, and other areas. Furthermore, the inherent organic nature, tailored pore structures, and adjustable chemical components of POPs offer a versatile platform for the incorporation of various metal active sites. Meticulously designed molecular building blocks can serve as organic ligands uniformly distributed throughout POPs, leading to the effective isolation of inorganic metal active sites at the molecular level. In this manner, POPs containing active metal centers bridge the gap between organic and inorganic scaffolds. This review aims to provide an overview of recent research progress on metal‐decorated POPs, focusing on strategies for incorporating metal active sites into POPs and their applications in adsorption, separation, catalysis, and photoelectrochemistry. Finally, current challenges and future prospects are discussed for further research. Key Scientists: Advanced functionalized porous organic polymers have become a new research hotspot, ranging from their construction to their use in gas storage and separation, catalysis, energy storage, electrochemistry, and other applications. In 2002, the McKeown group was the first to report phthalocyanine‐based MPOPs with permanent porosity and a moderate surface area. In 2010, the Yu group prepared nanoporous polyporphyrin materials P(Fe‐TTPP) from the metallated porphyrin with functionalized thiophenyl groups by the FeCl3 catalyzed oxidation couple reaction showing the surface area of 1522 m2·g–1. Subsequently, in 2013, the Deng group was the first to use metalated salens as the original building blocks for preparing MPOPs. The Morin group was the first to produce a series of ferrocene‐based nanoporous frameworks via radical polymerization, with surface areas ranging from 385 to 899 m2·g–1. In 2016, the Han group synthesized two N‐pyridinylphenylcarbazole (PPC) ligands to produce a series of metalized polycarbazole networks. Recently, the Tan group reported a solvent‐knitting hyper‐cross‐linking reaction to produce HUST‐1, which contains a porphyrin unit. The porphyrin moiety provides a centered square‐planar metal post‐coordination site, resulting in the metalated HUST‐1‐Co, which exhibits high efficiency in the catalytic conversion of CO2. Additionally, the Kegnæs group combined the decomposition of the palladium complex with an in situ catalyzed polymerization reaction, enabling the confinement of nascent Pd particles in the developing polymer network. This review focuses on recent research progress in metal‐decorated POPs, emphasizing strategies for incorporating metal active sites into POPs and their applications. [ABSTRACT FROM AUTHOR]

Covalent cross-linked porous organic polymers (POPs) have shown great potential in adsorption and separation fields owing to their high surface areas, easy functionalization, and porous design using synthetic strategies. Herein, we report the facile preparation of two triphenylamine-based nitrogen-rich porous organic polyaminals (TPOAs), denoted as TPOA-F and TPOA-OH, from triphenylamine-based triazine-hexamine and commercially available fluorine- and hydroxyl-monoaldehydes, respectively via a amine–aldehyde condensation reaction without any catalyst addition. These two resulting TPOAs possessed large specific surface areas (1179 and 565 m2 g−1) and hierarchical pore distribution (0.58 to 5.20 nm). Owing to this, TPOAs exhibited highly promising application potential for natural gas purification (mainly light hydrocarbons and CO2 separation). Among them, TPOA-F shows the highest C3H8 uptake of 225 mg g−1, C2H6 uptake of 122 mg g−1, and CO2 uptake of 155 mg g−1 at 273 K/1 bar and C3H8 uptake of 187 mg g−1, C2H6 uptake of 93 mg g−1, and CO2 uptake of 95 mg g−1 at 298 K/1 bar. Then, the C3H8/CH4, C2H6/CH4, C3H8/C2H6, C3H8/CO2, C2H6/CO2, and CO2/CH4 gas mixture adsorption selectivities for TPOAs demonstrated the values of 68.7–78.8, 14.0–15.7, 4.9–5.0, 16.5–17.4, 3.4–3.5, and 4.2–4.5. Meanwhile, TPOAs also displayed considerable iodine capture performance up to 3.43 g g−1. In addition, this has surpassed many reported porous polyaminal materials for their abundant porosity and nitrogen active sites, which offer host–guest interactions due to the high electron density. This study would provide valuable guidance for the development and application of efficient POP-based adsorption and separation materials. [ABSTRACT FROM AUTHOR]

High processing viscosity and poor solubility limit the application of heterocyclic polymers for fabricating organic wavetransparent composites for aerospace applications. In this paper, a novel resin, poly(phthalazinone ether bisphenol fluorene) encapped with phthalonitrile (PPEBF-Ph), was synthesized and used as the matrix. Biphenol-based phthalonitrile monomer BP-Ph was also synthesized and blended with PPEBF-Ph to further lower the processing viscosity. Solubility tests showed that the resin was soluble in dimethylformamide, N,N-dimethyl acetamide, N-methylpyrrolidone, dimethyl sulfoxide, chloroform, and other solvents. Differential scanning calorimetry and rheological studies revealed that the mixed resins exhibited low processing viscosity and a wide processing window below the gel temperature. Thermogravimetric analysis indicated that the cured resins were stable below 510-530 8C under nitrogen atmosphere after 6 h of curing (decreased by 40-60% compared with previous reports on phthalonitrile resin). In air, the char yields of the resins reached 20-30% when heated at 800 °C. The composites were reinforced by a quartz fiber cloth and exhibited a dielectric constant of 2.94-3.27 in an electromagnetic field with frequency ranging from 8 to 18 GHz. Retention of the bending modulus exceeded 70% at 400 °C according to dynamic mechanical analysis, indicating excellent mechanical stability was obtained. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Advanced functionalization‐decorated porous organic polymers (POPs) are emerging as a prominent research focus, spanning from their construction to applications in gas storage and separation, catalysis, energy storage, electrochemistry, and other areas. Furthermore, the inherent organic nature, tailored pore structures, and adjustable chemical components of POPs offer a versatile platform for the incorporation of various metal active sites. Meticulously designed molecular building blocks can serve as organic ligands uniformly distributed throughout POPs, leading to the effective isolation of inorganic metal active sites at the molecular level. In this manner, POPs containing active metal centers bridge the gap between organic and inorganic scaffolds. This review aims to provide an overview of recent research progress on metal‐decorated POPs, focusing on strategies for incorporating metal active sites into POPs and their applications in adsorption, separation, catalysis, and photoelectrochemistry. Finally, current challenges and future prospects are discussed for further research. Key Scientists: Advanced functionalized porous organic polymers have become a new research hotspot, ranging from their construction to their use in gas storage and separation, catalysis, energy storage, electrochemistry, and other applications. In 2002, the McKeown group was the first to report phthalocyanine‐based MPOPs with permanent porosity and a moderate surface area. In 2010, the Yu group prepared nanoporous polyporphyrin materials P(Fe‐TTPP) from the metallated porphyrin with functionalized thiophenyl groups by the FeCl3 catalyzed oxidation couple reaction showing the surface area of 1522 m2·g–1. Subsequently, in 2013, the Deng group was the first to use metalated salens as the original building blocks for preparing MPOPs. The Morin group was the first to produce a series of ferrocene‐based nanoporous frameworks via radical polymerization, with surface areas ranging from 385 to 899 m2·g–1. In 2016, the Han group synthesized two N‐pyridinylphenylcarbazole (PPC) ligands to produce a series of metalized polycarbazole networks. Recently, the Tan group reported a solvent‐knitting hyper‐cross‐linking reaction to produce HUST‐1, which contains a porphyrin unit. The porphyrin moiety provides a centered square‐planar metal post‐coordination site, resulting in the metalated HUST‐1‐Co, which exhibits high efficiency in the catalytic conversion of CO2. Additionally, the Kegnæs group combined the decomposition of the palladium complex with an in situ catalyzed polymerization reaction, enabling the confinement of nascent Pd particles in the developing polymer network. This review focuses on recent research progress in metal‐decorated POPs, emphasizing strategies for incorporating metal active sites into POPs and their applications. [ABSTRACT FROM AUTHOR]

Five porous ether-linked phthalazinone-based covalent triazine frameworks (PHCTFs) were successfully constructed via ionothermal polymerizations from flexible dicyano monomers containing asymmetric, twisted, and N-heterocyclic phthalazinone structure. All the building blocks could be easily prepared by simple and low-cost aromatic nucleophilic substitution reactions, showing the large-scale application potential of thermal stable phthalazinone structure in constructing porous materials. Generally, the flexible building blocks are avoided to prevent the networks from collapsing in constructing high surface area porous materials. Our experimental results revealed that the introduction of the substituents can effectively decrease the probability of the network interpenetration from the longer struts and the intermolecular/intramolecular intercalation from the increased degree of conformation freedom in the flexible ether-linkage, the BET surface areas of PHCTFs increasing from 676 to 1270 m 2 g -1 . Meanwhile, the effects of introducing different sizes (methyl or phenyl group) and amounts (one or two) of substituents on the porosities of the target polymer networks were also investigated in detail. The high CO 2 adsorption capacity of 10.3 wt % (273 K, 1 bar) can be ascribed to the strong affinity of the electron-rich N,O-containing networks with CO 2 . Excitingly, PHCTF-5 demonstrates the high CO 2 /N 2 selectivity up to 138 (273 K, 1 bar), according to the ideal adsorbed solution theory (IAST) for the higher proportion of V micro accompanied the electron-rich heteroatoms characteristic. Such high CO 2 adsorption capacity and good separation properties are superior to those of many other microporous organic polymers. These properties along with easily up-scalable synthesis make porous PHCTFs promising candidates applied in gas sorption and separation field.