A Triphenylphosphine-Based Microporous Polymer for a Wittig Reaction Cycle in the Solid State.

The Wittig reaction is a key step in industrial processes to synthesise large quantities of vitamin A and various other important chemicals that are used in daily life. This article presents a pathway to achieve the Wittig reaction in a solid network. A highly porous triphenylphosphine-based polymer was applied as a solid Wittig reagent that undergoes, in a multi-step cycle, in total six post-synthetic modifications. This allowed for regeneration of the solid Wittig reagent and reuse for the same reaction cycle. Of particular industrial relevance is that the newly developed material also enables a simple way of separating the product by filtration. Therefore, additional costly and difficult separation and purification steps are no longer needed.

Eutectic Media Open a Synthetic Route to Oligocitrazinic Acid Fluorophores of Purple Hue.

Under isochoric and solvent-free conditions, the reaction between ammonium formate and citric acid results in a deeply purple reaction product with fluorescent properties. This brings this reaction in the realm of bio-based fluorophores and bottom-up carbon nanodots from citric acid. The reaction conditions are optimized in terms of UV-vis spectroscopic properties and, subsequently, the main reaction product is separated. While the structural analysis does not give any indication for carbon nanodots in a general sense, it points towards the formation of molecular fluorophores that consist of oligomerized citrazinic acid derivatives. Furthermore, EPR spectroscopy reveals the presence of stable free radicals in the product. We hypothesize that such open-shell structures may play a general role in molecular fluorophores from citric acid and are not yet sufficiently explored. Therefore, we believe that analysis of these newly discovered fluorophores may contribute to a better understanding of the properties of fluorophores and CND from citric acid in general.

Linker Exchange as Facile Method for Post-Synthetic Modification of ß-Ketoenamine-linked Covalent Organic Frameworks.

Post-synthetic linker exchange performed on covalent organic frameworks (COFs) has become an important method to introduce functional building blocks into their backbone and thus to tune their chemical and physical properties. However, the linker exchange method has so far only been described for COFs with relatively weak linkages like imines. Herein, it is shown that this method can be also used for a post-synthetic linker exchange reaction on a ß-ketoenamine linked COF. The time needed to achieve considerable linker exchange is much prolonged compared to other COFs with less stable linkages, however, this enables to achieve very good control on the ratio of the respective building blocks within the framework.

Integrating Bifunctionality and Chemical Stability in Covalent Organic Frameworks via One-Pot Multicomponent Reactions for Solar-Driven H2O2 Production.

Multicomponent reactions (MCRs) can be used to introduce different functionalities into highly stable covalent organic frameworks (COFs). In this work, the irreversible three-component Doebner reaction is utilized to synthesize four chemically stable quinoline-4-carboxylic acid DMCR-COFs (DMCR-1-3 and DMCR-1NH) equipped with an acid-base bifunctionality. These DMCR-COFs show superior photocatalytic H2O2 evolution (one of the most important industrial oxidants) compared to the imine COF analogue (Imine-1). This is achieved with sacrificial oxidants but also in pure water and under an oxygen or air atmosphere. Furthermore, the DMCR-COFs show high photostability, durability, and recyclability. MCR-COFs thus provide a viable materials' platform for solar to chemical energy conversion.

Programmable Photocatalytic Activity of Multicomponent Covalent Organic Frameworks Used as Metallaphotocatalysts.

The multicomponent approach allows to incorporate several functionalities into a single covalent organic framework (COF) and consequently allows the construction of bifunctional materials for cooperative catalysis. The well-defined structure of such multicomponent COFs is furthermore ideally suited for structure-activity relationship studies. We report a series of multicomponent COFs that contain acridine- and 2,2'-bipyridine linkers connected through 1,3,5-benzenetrialdehyde derivatives. The acridine motif is responsible for broad light absorption, while the bipyridine unit enables complexation of nickel catalysts. These features enable the usage of the framework materials as catalysts for light-mediated carbon-heteroatom cross-couplings. Variation of the node units shows that the catalytic activity correlates to the keto-enamine tautomer isomerism. This allows switching between high charge-carrier mobility and persistent, localized charge-separated species depending on the nodes, a tool to tailor the materials for specific reactions. Moreover, nickel-loaded COFs are recyclable and catalyze cross-couplings even using red light irradiation.

Intraligand Charge Transfer Enables Visible-Light-Mediated Nickel-Catalyzed Cross-Coupling Reactions.

We demonstrate that several visible-light-mediated carbon-heteroatom cross-coupling reactions can be carried out using a photoactive NiII precatalyst that forms in situ from a nickel salt and a bipyridine ligand decorated with two carbazole groups (Ni(Czbpy)Cl2 ). The activation of this precatalyst towards cross-coupling reactions follows a hitherto undisclosed mechanism that is different from previously reported light-responsive nickel complexes that undergo metal-to-ligand charge transfer. Theoretical and spectroscopic investigations revealed that irradiation of Ni(Czbpy)Cl2 with visible light causes an initial intraligand charge transfer event that triggers productive catalysis. Ligand polymerization affords a porous, recyclable organic polymer for heterogeneous nickel catalysis of cross-coupling reactions. The heterogeneous catalyst shows stable performance in a packed-bed flow reactor during a week of continuous operation.

Metal-Assisted and Solvent-Mediated Synthesis of Two-Dimensional Triazine Structures on Gram Scale.

Covalent triazine frameworks are an emerging material class that have shown promising performance for a range of applications. In this work, we report on a metal-assisted and solvent-mediated reaction between calcium carbide and cyanuric chloride, as cheap and commercially available precursors, to synthesize two-dimensional triazine structures (2DTSs). The reaction between the solvent, dimethylformamide, and cyanuric chloride was promoted by calcium carbide and resulted in dimethylamino-s-triazine intermediates, which in turn undergo nucleophilic substitutions. This reaction was directed into two dimensions by calcium ions derived from calcium carbide and induced the formation of 2DTSs. The role of calcium ions to direct the two-dimensionality of the final structure was simulated using DFT and further proven by synthesizing molecular intermediates. The water content of the reaction medium was found to be a crucial factor that affected the structure of the products dramatically. While 2DTSs were obtained under anhydrous conditions, a mixture of graphitic material/2DTSs or only graphitic material (GM) was obtained in aqueous solutions. Due to the straightforward and gram-scale synthesis of 2DTSs, as well as their photothermal and photodynamic properties, they are promising materials for a wide range of future applications, including bacteria and virus incapacitation.