Linkage Transformations in a Three-Dimensional Covalent Organic Framework for High-Capacity Adsorption of Perfluoroalkyl Substances.

Despite their many advantages, covalent organic frameworks (COFs) built from three-dimensional monomers are synthetically difficult to functionalize. Herein, we provide a new synthetic approach to the functionalization of a three-dimensional covalent organic framework (COF-300) by using a series of solid-state linkage transformations. By reducing the imine linkages of the framework to amine linkages, we produced a more hydrolytically stable material and liberated a nucleophilic amino group, poised for further functionalization. We then treated the amine-linked COF with diverse electrophiles to generate a library of functionalized materials, which we tested for their ability to adsorb perfluoroalkyl substances (PFAS) from water. The framework functionalized with dimethylammonium groups, COF-300-dimethyl, adsorbed more than 250 mg of perfluorooctanoic acid (PFOA) per 1 g of COF, which represents an approximately 14,500-fold improvement over that of COF-300 and underscores the importance of electrostatic interactions to PFAS adsorption performance. This work provides a conceptually new approach to the design and synthesis of functional three-dimensional COFs.

Lamp vs Laser: A Visible Light Photoinitiator That Promotes Radical Polymerization at Low Intensities and Cationic Polymerization at High Intensities.

A visible light absorbing anthraquinone derivative 1-tosyloxy-2-methoxy-9,10-anthraquinone (QT) mediates both cationic and radical polymerizations depending on the intensity of visible light used. A previous study showed that this initiator generates para-toluenesulfonic acid through a stepwise, two-photon excitation mechanism. Thus, under high-intensity irradiation, QT generates acid in sufficient quantities to catalyze the cationic ring-opening polymerization of lactones. However, under low-intensity (lamp) conditions, the two-photon process is negligible, and QT photooxidizes DMSO, generating methyl radicals which initiate the RAFT polymerization of acrylates. This dual capability was utilized to switch between radical and cationic polymerizations to synthesize a copolymer using a one-pot procedure.

Elucidating complex triplet-state dynamics in the model system isopropylthioxanthone.

We introduce techniques for probing the dynamics of triplet states. We employ these tools, along with conventional techniques, to develop a detailed understanding of a complex chemical system: a negative-tone, radical photoresist for multiphoton absorption polymerization in which isopropylthioxanthone (ITX) is the photoinitiator. This work reveals that the same color of light used for the 2-photon excitation of ITX, leading to population of the triplet manifold through intersystem crossing, also depletes this triplet population via linear absorption followed by reverse intersystem crossing (RISC). Using spectroscopic tools and kinetic modeling, we identify the reactive triplet state and a non-reactive reservoir triplet state. We present compelling evidence that the deactivation channel involves RISC from an excited triplet state to a highly vibrationally excited level of the electronic ground state. The work described here offers the enticing possibility of understanding, and ultimately controlling, the photochemistry and photophysics of a broad range of triplet processes.

Templated synthesis enhances the cobalt adsorption capacity of a porous organic polymer.

Divalent transition metals such as Co(II) are important targets for removal from water sources, due to their potential toxicity as well as their high value. In this study, we found that a series of porous organic polymers based on amide-linked tetraphenylmethane units are effective Co(II) ion adsorbents in aqueous solution. To increase the density of Co(II) binding sites, we then developed a templated synthesis in which the branched, rigid monomers are pre-assembled around Co(II) ions prior to polymerization. After polymer formation, the Co(II) template ions are removed to yield a material rich in Co(II) binding sites. Ion adsorption isotherms show that the Co(II)-templated material has an ion adsorption capacity significantly greater than those of the non-templated materials, highlighting the utility of a templated synthetic route. SEM and TEM images show the morphology of the templated polymer to be dramatically different from the non-templated polymers and to be similar in size and shape to the Co(II)-monomer precursors, emphasizing the role of the template ions in directing the formation of the resulting polymer. This guest-templated approach requires no functionalization of the generic monomer and represents a promising synthetic route to high-capacity ion adsorbents for water purification and aqueous separations.

Photoacid Generators Activated through Sequential Two-Photon Excitation: 1-Sulfonatoxy-2-alkoxyanthraquinone Derivatives.

Two sulfonate ester derivatives of anthraquinone, 1-tosyloxy-2-methoxy-9,10-anthraquinone (1a) and 1-trifluoromethylsulfonoxy-2-methoxy-9,10-anthraquinone (1b), were prepared and their ability to produce strong acids upon photoexcitation was examined. It is shown that these compounds generate acid with a yield that increases with light intensity when the applied photon dose is held constant. Additional experiments show that the rate of acid generation increases fourfold when visible light (532 nm) laser pulses are combined with ultraviolet (355 nm) compared with ultraviolet alone. Continuous wave diode laser photolysis also affects acid generation with a rate that depends quadratically on the light intensity. Density functional theory calculations, laser flash photolysis, and chemical trapping experiments support a mechanism, whereby an initially formed triplet state (T1) is excited to a higher triplet state which in turn undergoes homolysis of the RS(O2)-OAr bond. Secondary reactions of the initially formed sulfonyl radicals produce strong acids. It is demonstrated that high-intensity photolysis of either 1a or 1b can initiate cationic polymerization of ethyl vinyl ether.

Visible-Light Photocatalytic Oxidation of DMSO for RAFT Polymerization.

The solvent is an important, yet often forgotten part of a reaction mechanism. Many photochemical polymerizations are carried out using dimethyl sulfoxide (DMSO) as a way to promote the solubility of both the reactants and products, but its reactivity is rarely considered when initiation mechanisms are proposed. Herein, the oxidation of DMSO by an excited-state quinone is used to form initiating radicals resulting in the polymerization of methacrylate monomers, and the polymerization can be controlled with the addition of a chain transfer agent. This process leads to the formation of polymers with narrow molecular weight distribution, and the polymerization is able to be carried out in the presence of oxygen. A visible light absorbing substituted anthraquinone is synthesized, and nanosecond transient absorption spectroscopy is used to monitor the intermediates involved in the initiation mechanism. Photoproduct analysis indicates formation of methyl radicals as a result of DMSO oxidation. Furthermore, we show that the solvent outcompetes the chain transfer agent for interacting with the excited-state anthraquinone. These observations have a broad impact on photoinduced polymerizations performed in DMSO as many photocatalysts are strong oxidants in the excited state and are capable of reacting with the solvent. Therefore, the role of the solvent needs to be more carefully considered when proposing mechanisms for photoinduced polymerizations in DMSO.

Generation of N,N-Di(4-bromophenyl)nitrenium Ion under Acidic Conditions: Search for a Nitrenium Dication.

The behavior of the N,N-di(4-bromophenyl)nitrenium ion under acidic aqueous conditions was examined via laser flash photolysis experiments. A long-lived species forms and can be assigned as the cation radical or the dication. This species is unreactive toward nucleophiles and reactive toward strong electron donors, consistent with a cation radical. Mechanistic analysis indicates that its formation is through a separate pathway compared to that of the nitrenium ion, suggestive of a triplet mechanism.

Mechanism of the photorelease of alcohols from the 9-phenyl-9-tritylone protecting group.

The 9-phenyl-9-tritylone photoremovable protecting group was examined using both photoproduct analysis and laser flash photolysis in order to determine the details of its mechanism of alcohol release. It is shown that formation of the tritylone anion radical is required for alcohol release. Attempts to trigger release via intramolecular photoinduced electron transfer were unsuccessful due to rapid back electron transfer reactions of the triplet diradical anion.