In dynamic covalent synthesis, kinetic traps are perceived as disadvantageous, hindering the system from reaching its thermodynamic equilibrium. Here we present the near-quantitative preparation of tetrahedral cages from simple tritopic precursors using alkyne metathesis. While the cages are the presumed thermodynamic sink, we experimentally demonstrate that the products no longer exchange their vertices once they have formed. The example reported here illustrates that kinetically trapped products may facilitate high yields of complex products from dynamic covalent synthesis.

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Per-and polyfluoroalkyl substances (PFAS) are widely used industrial chemicals that are of a great concern because of their pervasive presence in water resources and association with negative health effects. Crosslinked β-cyclodextrin-containing (β-CD) polymer adsorbents have shown promising performances for sequestering PFAS. Recently, installing amino groups into the crosslinkers of a β-CD polymer network improved the binding of many anionic PFAS, including short-chain and branched derivatives. However, the relative importance of the electrostatic interactions from the amino groups and the host-guest interactions within the cavity of the β-CD for PFAS binding are unclear. Herein, β-CD-based adsorbents crosslinked with tripodal crosslinkers containing three amino or amido groups are prepared with comparable physicochemical properties to investigate the respective roles of the crosslinker and β-CD in binding affinity and capacity for anionic PFAS. β-CD polymers containing amines showed superior removal for ten anionic PFAS compared to polymers containing amido groups. Both β-CD polymers have superior performance for perfluorooctanoic acid (PFOA) removal compared to activated carbons (ACs), consistent with β-CD:PFOA inclusion complexes playing an important role. Adsorbents containing amido groups showed low binding affinity and capacity for GenX, whereas the amine-functionalized polymer had outstanding affinity and capacity for GenX (K L = 8.8 × 10 4 M −1 , Q M = 222 mg g −1 ), underscoring the essential role of electrostatic interactions for removing short-chain and branched PFAS. The amine-containing β-CD polymer exhibited 100-fold higher affinity and twice the capacity (K L = 1.8 × 10 6 M −1 , Q M = 457 mg g −1 ) for PFOA compared to GenX, which are the highest reported values for β-CD polymers. These results highlight the synergistic effects of electrostatic interactions and host-guest interactions in β-CD polymers as important design criteria for efficient removal of anionic PFAS from water. This study further demonstrates broad tunability of crosslinked β-CD polymers and their promise as adsorbents for PFAS remediation.

We present here hexagonal tiling using hexagonal phenylene-ethynylene and phenylene-butadiynylene macrocycles attached by alkyl ester groups, PEM-C6 and PBM-C8, respectively, or triethylene glycol ester groups, PEM-TEG and PBM-TEG, respectively, at each vertex of the macrocyclic periphery at the liquid/solid interface. In this study, we focused on the effects of macrocyclic core size and the chemical properties of side chains attached to macrocyclic cores as well as solute concentrations on the hexagonal geometry of self-assembled monolayers. STM observations at the 1,2,4-trichrolobenzene/graphite interface revealed that PEM-C6 formed a honeycomb structure by van der Waals interactions between the interdigitated alkyl chains. However, upon increasing solute concentration, it changed to more dense hexagonal structure (tentatively called loose hexagonal structure I). In contrast, PBM-C8 formed loose hexagonal structure II of a slightly different packing mode at low concentration, while at high concentration it formed a high-density hexagonal structure in which alkyl chains are not adsorbed on the surface (dense hexagonal structure). In the dense hexagonal structure, macrocyclic cores are linked by hydrogen bonds between the ester carbonyl oxygen and the aromatic hydrogen atoms of the neighboring macrocycles. The packing geometries of loose hexagonal structures of PEM-C6 and PBM-C8 are different due to the different distance between the attachment of the alkyl ester groups which are located in confined space. On the other hand, PEM-TEG and PBM-TEG formed dense hexagonal structures, similar to PBM-C8 at high concentration, with their TEG units not adsorbed on the surface.

Covalent organic frameworks (COFs) generally leverage one or two monomers with specific sizes and shapes to access highly symmetric and periodic polymer networks. Almost all reported COFs employ the minimum sets of monomers needed for the polymerization (usually two, sometimes one) and crystallize in high-symmetry topologies. COFs synthesized from more than two monomers usually employ mixtures with different pendant functionalities to distribute these groups statistically throughout the structure, or monomers with different sizes in ratios targeting lower symmetry topologies. Here, we demonstrate that mixtures of monomers with different lengths generate single-phase, hexagonal two-dimensional covalent organic framework (2D COF) solid solutions at continuously variable feed ratios. X-ray diffraction measurements, Fourier-transform infrared spectroscopy, and Pawley refinement indicate that both monomers distribute randomly within the same lattice, and the lattice parameters continuously increase as more of the larger linker is incorporated. Furthermore, COF solid solutions are accessed directly by polymerizing a mixture of monomers but not via linker exchange from a preformed COF. As strain develops from the lattice accommodating monomers with different sizes, the nonlinear relationship between the monomer incorporation and the COF's lattice parameters suggests that bond-bending of the monomers plays a role in incorporating monomers of different lengths into the solid solutions. Solid solution formation represents a new strategy to design 2D COFs and increase their complexity. Specifically, varying the monomer composition of a given network enables many properties, such as the average pore size, to be continuously tuned between those of corresponding pure COFs.

In the dynamic synthesis of covalent organic frameworks and molecular cages, the typical synthetic approach involves heuristic methods of discovery. While this approach has yielded many remarkable products, the ability to predict the structural outcome of subjecting a multitopic precursor to dynamic covalent chemistry (DCC) remains a challenge in the field. The synthesis of covalent organic cages is a prime example of this phenomenon, where precursors designed with the intention of affording a specific product may deviate dramatically when the DCC synthesis is attempted. As such, rational design principles are needed to accelerate discovery in cage synthesis using DCC. Herein, we test the hypothesis that precursor bite angle contributes significantly to the energy landscape and product distribution in multitopic alkyne metathesis (AM). By subjecting a series of precursors with varying bite angles to AM, we experimentally demonstrate that the product distribution, and convergence toward product formation, is strongly dependent on this geometric attribute. Surprisingly, we discovered that precursors with the ideal bite angle (60°) do not afford the most efficient pathway to the product. The systematic study reported here illustrates how seemingly minor adjustments in precursor geometry greatly affect the outcome of DCC systems. This research illustrates the importance of fine-tuning precursor geometric parameters in order to successfully realize desirable targets.

Disinfection byproducts such as trihalomethanes are commonly found in drinking water. Trihalomethanes are formed upon chlorination of natural organic matter found in many drinking water sources. Inspired by molecular CHCl3⊂cavitand host–guest complexes, we designed porous polymers composed of resorcinarene receptors. These materials show higher affinity for halomethanes than a specialty activated carbon used for trihalomethane removal. The cavitand polymers show similar removal kinetics as activated carbon and have high capacity (49 mg g–1 of CHCl3). These materials maintain their performance in drinking water and can be thermally regenerated. Cavitand polymers also outperform commercial resins for 1,4-dioxane adsorption, which contaminates many water sources. These materials show promise for water treatment and demonstrate the value of using supramolecular receptors to design adsorbents for water purification.

Chemical nerve agents employed in warfare can induce paralysis and death within minutes of exposure. Zirconium-based metal–organic frameworks (MOFs), such as UiO-66-NH2, show promise for the fast and efficient decontamination of nerve agents, which motivates their incorporation into textiles as protective layers. Few scalable methods to produce MOF/textile composites for personal protective applications have been developed; however, they mainly require the use of toxic and flammable solvents. Here, we describe a scalable, single-step method to synthesize UiO-66-NH2 on cotton fabrics by hot pressing the monomers onto the fabric samples. The use of a preformed hexanuclear zirconium benzoate cluster with 1,8-bis­(dimethylamine)­naphthalene as a non-nucleophilic base improved the quality of MOFs synthesized from the hot press method, as determined by an increase in their surface area and crystallinity. Preactivation of the cotton fabric with carboxylic acids provided UiO-66-NH2/cotton composites of high MOF loadings with homogeneous coverage, which demonstrated efficient decontamination of a nerve agent simulant, dimethyl-4-nitrophenyl phosphate (DMNP).