UV-to-NIR Harvesting Conjugated Porous Polymer Nanocomposite: Upconversion and Plasmon Expedited Thioether Photooxidation.

Photocatalysts capable of harvesting a broad range of the solar spectrum are essential for sustainable chemical transformations and environmental remediation. Herein, we have integrated NIR-absorbing upconversion nanoparticles (UCNP) with UV-Vis absorbing conjugated porous organic polymer (POP) through the in situ multicomponent C-C coupling to fabricate a UC-POP nanocomposite. The light-harvesting ability of UC-POP is further augmented by loading plasmonic gold nanoparticles (AuNP) into UC-POP. A three-times enhancement in the upconversion luminescence is observed upon the incorporation of AuNP in UC-POP, subsequently boosting the photocatalytic activity of UC-POP-Au. The spectroscopic and photoelectrochemical investigations infer the enhanced photocatalytic oxidation of thioethers, including mustard gas simulant by UC-POP-Au compared to POP and UC-POP due to the facile electron-hole pair generation, suppressed exciton recombination, and efficient charge carrier migration. Thus, the unique design strategy of combining plasmonic and upconversion nanoparticles with a conjugated porous organic polymer opens up new vistas towards artificial light harvesting.

Structural Modulation of Nitrogen-Rich Covalent Organic Frameworks for Iodine Capture.

Developing efficient adsorbent materials for iodine scavenging is essential to mitigate the threat of radioactive iodine causing adverse effects on human health and the environment. In this context, we explored N-rich two-dimensional covalent organic frameworks (COFs) with diverse functionalities for iodine capture. The pyridyl-hydroxyl-functionalized triazine-based novel 5,5',5″-(1,3,5-triazine-2,4,6-triyl)tris(pyridine-2-amine) (TTPA)-COF possesses high crystallinity (crystalline domain size: 24.4 ± 0.6 nm) and high porosity (specific BET surface area: 1000 ± 90 m2 g-1). TTPA-COF exhibits superior vapor-phase iodine adsorption (4.43 ± 0.01 g g-1) compared to analogous COF devoid of pyridinic moieties, 2,4,6-tris(4-aminophenyl)-1,3,5-triazine (TAPT)-COF. The high iodine capture by TTPA-COF is due to the enhanced binding affinity conferred by the extra pyridinic active sites. Furthermore, the crucial role of long-range order in porous adsorbents has been experimentally evidenced by comparing the performance of iodine vapor capture of TTPA-COF with an amorphous network polymer having identical functionalities. We have also demonstrated the high iodine scavenging ability of TTPA-COF from the organic and aqueous phases. The mechanism of iodine adsorption by the heteroatom-rich framework is elucidated through FTIR, XPS, and Raman spectral analyses. The present study highlights the need for structural tweaking of the building blocks toward the rational construction of advanced functional porous materials for a task-specific application.

Pyridinium-Functionalized Ionic Porous Organic Polymer for Rapid Scavenging of Oxoanions from Water.

Metal oxoanions adversely affect the food chain through bioaccumulation and biomagnification. Therefore, they are among the major freshwater contaminants that require immediate remediation. Although several adsorbents are developed over the years for sequestering these micropollutants, the selective removal of oxoanions remains still a formidable challenge. Herein, pyridinium and triazine-based ionic porous organic polymer, iPOP-Cl, developed through a Brønsted acid-catalyzed aminal formation reaction, is reported as a suitable anion exchange material for the selective removal of metal oxoanions from wastewater. The positively charged nitrogen centers, along with exchangeable chloride counter-ions in the porous polymer, allow facile oxoanion uptake. iPOP-Cl is found to be a selective scavenger of permanganate (MnO4 - ) and dichromate (Cr2 O7 2- ) from water in the presence of a high concentration of competing anions generally found in brackish water. The material exhibits fast sorption kinetics, a high uptake capacity (333 mg g-1 for MnO4 - and 358 mg g-1 for Cr2 O7 2- ), and excellent recyclability.

Transformation of an Imine Cage to a Covalent Organic Framework Film at the Liquid-Liquid Interface.

Dynamic covalent chemistry (DCC) opens up a fascinating route for the construction of well-organized supramolecular architectures, starting from organic molecular cages to crystalline macromolecular covalent organic frameworks (COFs). Herein, for the first time, we have manifested a facile room-temperature DCC-directed transformation of discrete organic imine cage-to-COF film at the liquid-liquid interface. The unfolding of the cage leading to the generation of imine intermediates, followed by their interface-assisted preorganization and subsequent growth of the COF film, are elucidated through detailed spectroscopic and microscopic investigations. The interfacial cage-to-COF transformation provides a facile route for the faster fabrication of free-standing COF films with high porosity and crystallinity, demonstrating excellent performance towards molecular sieving and high solvent permeance. Thus, the current study opens up a new route for structural interconversion between two crystalline entities with diverse dimensionality employing DCC at the confined interface.

Porous Organic Polymers: Promising Testbed for Heterogeneous Reactive Oxygen Species Mediated Photocatalysis and Nonredox CO2 Fixation.

Catalysts play a pivotal role in achieving the global need for food and energy. In this context, porous organic polymers (POPs) with high surface area, robust architecture, tunable pore size, and chemical functionalities have emerged as promising testbeds for heterogeneous catalysis. Amorphous POPs having functionalized interconnected hierarchical porous structures activate a diverse range of substrates through covalent/non-covalent interactions or act as a host matrix to encapsulate catalytically active metal centers. On the other hand, conjugated POPs have been explored for photoinduced chemical transformations. In this personal account, we have delineated the evolution of various POPs and the specific role of pores and pore functionalities in heterogeneous catalysis. Subsequently, we retrospect our journey over the last ten years towards designing and fabricating amorphous POPs for heterogeneous catalysis, specifically photocatalytic reactive oxygen species (ROS)-mediated organic transformations and nonredox chemical fixation of CO2 . We have also outlined some of the future avenues of POPs and POP-based hybrid materials for diverse catalytic applications.

Nanostructured Hypercrosslinked Porous Organic Polymers: Morphological Evolution and Rapid Separation of Polar Organic Micropollutants.

Nanostructured hypercrosslinked porous organic polymers have triggered immense research interest for a broad spectrum of applications ranging from catalysis to molecular separation. However, it still remains a challenge to tune their nanoscale morphology. Herein, we demonstrated a remarkable variation of morphologies of triptycene-based hypercrosslinked microporous polymers starting from irregular aggregates (FCTP) to rigid spheres (SCTP) to two-dimensional nanosheets (SKTP) from three distinct polymerization methodologies, Friedel-Crafts knitting using an external crosslinker, Scholl reaction, and solvent knitting, respectively. Further, the dramatic role of reaction temperatures, catalysts, and solvents resulting in well-defined morphologies was elucidated. Mechanistic investigations coupled with microscopic and computational studies revealed the evolution of 2D nanosheets of a highly porous solvent-knitted polymer (SKTP, 2385 m2 g-1), resulting from the sequential hierarchical self-assembly of nanospheres and nanoribbons. A structure-activity correlation of hypercrosslinked polymers and their sulfonated counterparts for the removal of toxic polar organic micropollutants from water was delineated based on the chemical functionalities, specific surface area, pore size distribution, dispersity, and nanoscale morphology. Furthermore, a sulfonated 2D sheet-like solvent-knitted polymer (SKTPS) exhibited rapid adsorption kinetics (within 30 s) for a large array of polar organic micropollutants, including plastic components, steroids, antibiotic drugs, herbicides, and pesticides with remarkable uptake capacity and excellent recyclability. The current study provides the impetus for designing morphology-controlled functionalized porous polymers for task-specific applications.

N,N'-bicarbazole-benzothiadiazole-based conjugated porous organic polymer for reactive oxygen species generation in live cells.

A π-conjugated porous organic polymer (BCzBz) was fabricated employing N,N'-bicarbazole and benzothiadiazole as molecular building units exhibiting broad visible light absorption. The photostable, water-dispersible, and cytocompatible BCzBz was demonstrated as an efficient probe for intracellular reactive oxygen species generation under photoirradiation.

Porous noria polymer: a cage-to-network approach toward a robust catalyst for CO2 fixation and nitroarene reduction.

The advantages of the cage-to-network design strategy were demonstrated by knitting a waterwheel-like preporous molecular cage, noria, with a rigid aromatic linker to obtain a highly microporous organic polymer (NPOP, SBET: 748 ± 25 m2 g-1). The NPOP was employed for the catalytic conversion of CO2 to cyclic carbonates under solvent-free reaction conditions. Furthermore, a silver nanoparticle encapsulated NPOP exhibited remarkable catalytic activity for nitroarene reduction with excellent recyclability.

A Tailored Heptazine-Based Porous Polymeric Network as a Versatile Heterogeneous (Photo)catalyst.

A heptazine-based microporous polymeric network, HMP-TAPA was synthesised by direct coupling of trichloroheptazine and tris(4-aminophenyl)amine (TAPA). A high surface area of 424 m2 /g was achieved, which is the highest surface area among heptazine-based polymeric networks (HMPs). The tailored electron-donor and -acceptor units in HMP-TAPA give broad visible-light absorption. HMP-TAPA was employed as metal-free photocatalyst for oxidative coupling of amines to imines under visible light irradiation with 98 % selectivity. Furthermore, the surface basicity of HMP-TAPA was used to achieve metal-free heterogeneous base catalysis for Knoevenagel condensation under base-free conditions with >99 % conversion. In addition, HMP-TAPA showed extreme robustness over a wide pH range (1-14). The versatility and flexibility of the current material design is beneficial for understanding its photoactivity and surface basicity so as to design dual active (photo)catalyst materials for specific applications.

Cavitand and Molecular Cage-Based Porous Organic Polymers.

Supramolecular cavitands and organic cages having a well-defined cavity and excellent host-guest complexing ability have been explored for a myriad of applications ranging from catalysis to molecular separation to drug delivery. On the other hand, porous organic polymers (POPs) having tunable porosity and a robust network structure have emerged as advanced materials for molecular storage, heterogeneous catalysis, water purification, light harvesting, and energy storage. A fruitful marriage between guest-responsive discrete porous supramolecular hosts and highly porous organic polymers has created a new interface in supramolecular chemistry and materials science, confronting the challenges related to energy and the environment. In this mini-review, we have addressed the recent advances (from 2015 to the middle of 2020) of cavitand and organic cage-based porous organic polymers for sustainable development, including applications in heterogeneous catalysis, CO2 conversion, micropollutant separation, and heavy metal sequestration from water. We have highlighted the "cavitand/cage-to-framework" design strategy and delineated the future scope of the emerging new class of porous organic networks from "preporous" building blocks.

Multifunctional ionic porous frameworks for CO2 conversion and combating microbes.

Porous organic frameworks (POFs) with a heteroatom rich ionic backbone have emerged as advanced materials for catalysis, molecular separation, and antimicrobial applications. The loading of metal ions further enhances Lewis acidity, augmenting the activity associated with such frameworks. Metal-loaded ionic POFs, however, often suffer from physicochemical instability, thereby limiting their scope for diverse applications. Herein, we report the fabrication of triaminoguanidinium-based ionic POFs through Schiff base condensation in a cost-effective and scalable manner. The resultant N-rich ionic frameworks facilitate selective CO2 uptake and afford high metal (Zn(ii): 47.2%) loading capacity. Owing to the ionic guanidinium core and ZnO infused mesoporous frameworks, Zn/POFs showed pronounced catalytic activity in the cycloaddition of CO2 and epoxides into cyclic organic carbonates under solvent-free conditions with high catalyst recyclability. The synergistic effect of infused ZnO and cationic triaminoguanidinium frameworks in Zn/POFs led to robust antibacterial (Gram-positive, Staphylococcus aureus and Gram-negative, Escherichia coli) and antiviral activity targeting HIV-1 and VSV-G enveloped lentiviral particles. We thus present triaminoguanidinium-based POFs and Zn/POFs as a new class of multifunctional materials for environmental remediation and biomedical applications.

Molecular Engineering Approaches Towards All-Organic White Light Emitting Materials.

White light emitting (WLE) materials are of increasing interest owing to their promising applications in artificial lighting, display devices, molecular sensors, and switches. In this context, organic WLE materials cater to the interest of the scientific community owing to their promising features like color purity, long-term stability, solution processability, cost-effectiveness, and low toxicity. The typical method for the generation of white light is to combine three primary (red, green, and blue) or the two complementary (e.g., yellow and blue or red and cyan) emissive units covering the whole visible spectral window (400-800 nm). The judicious choice of molecular building blocks and connecting them through either strong covalent bonds or assembling through weak noncovalent interactions are the key to achieve enhanced emission spanning the entire visible region. In the present review article, molecular engineering approaches for the development of all-organic WLE materials are analyzed in view of different photophysical processes like fluorescence resonance energy transfer (FRET), excited-state intramolecular proton transfer (ESIPT), charge transfer (CT), monomer-excimer emission, triplet-state harvesting, etc. The key aspect of tuning the molecular fluorescence under the influence of pH, heat, and host-guest interactions is also discussed. The white light emission obtained from small organic molecules to supramolecular assemblies is presented, including polymers, micelles, and also employing covalent organic frameworks. The state-of-the-art knowledge in the field of organic WLE materials, challenges, and future scope are delineated.

A smart photosensitizer based on a red emitting solution processable porous polymer: generation of reactive oxygen species.

A novel approach for the fabrication of a solution processable conjugated porous organic polymer (CzBDP) involving a flexible core composed of carbazole and boron dipyrromethene was developed. The red emitting soluble polymer was found to be an excellent probe for the generation of both singlet oxygen and superoxide anion radicals under visible light irradiation.