In recent decades, 3D printing (also known as additive manufacturing) techniques have moved beyond their traditional applications in the fields of industrial manufacturing and prototyping to increasingly find roles in scientific research contexts, such as synthetic chemistry. We present a general approach for the production of bespoke chemical reactors, termed reactionware, using two different approaches to extrusion-based 3D printing. This protocol describes the printing of an inert polypropylene (PP) architecture with the concurrent printing of soft material catalyst composites, using two different 3D printer setups. The steps of the PROCEDURE describe the design and preparation of a 3D digital model of the desired reactionware device and the preparation of this model for use with fused deposition modeling (FDM) type 3D printers. The protocol then further describes the preparation of composite catalyst-silicone materials for incorporation into the 3D-printed device and the steps required to fabricate a reactionware device. This combined approach allows versatility in the design and use of reactionware based on the specific needs of the experimental user. To illustrate this, we present a detailed procedure for the production of one such reactionware device that will result in the production of a sealed reactor capable of effecting a multistep organic synthesis. Depending on the design time of the 3D model, and including time for curing and drying of materials, this procedure can be completed in ∼3 d.

A series of tripodal alcohols substituted Anderson-type polyoxometalates (POMs) including mono-substituted (compounds and ), asymmetrical bi-substituted (compound ), and symmetrical bi-substituted ones (compounds and ) have been synthesized under hydrothermal conditions using a pre-designed step-by-step strategy, and compounds , and have been fully characterized by single-crystal X-ray diffraction, ESI-MS, and elemental analysis.

Polyoxometalates (POMs) have been found to be good end-capping ligands for gold nanoparticles (AuNPs). Herein we introduce a new synthetic method to synthesize gold nanoparticle-POM hybrids by heating a solution of AuNO3(PMe3) in acetonitrile in the presence of appropriate POM species with tetrabutyl-ammonium (TBA) as a countercation at 120 o C in a microwave. This method allowed us to produce POM-capped AuNPs without over reduction of the solution causing decomposition or reorganization of the POMs. Analysis of the resulting material by TEM showed that the POM's size, charge and functionality are key factors controlling the resulting POM-AuNP hybrid structure. Additionally, the reaction was monitored by ESI-MS, UV-Vis spectroscopy and DLS. The ESI-MS studies reveal crucial information regarding the nature of the reaction that takes place, showing the cation-exchange between Au(I) and tetrabutyl-ammonium (TBA) cations, followed by self-reduction of the Me3PAu(I)-POM complex.

Integrating different types of supramolecular interactions opens the possibility to generate nanoparticle surfactants (NPSs) at the liquid-liquid interface that are responsive to multiple stimuli. Here we develop a covalently modified polyoxometalate/β-cyclodextrin (POM/β-CD) organic-inorganic hybrid, consisting of a negatively charged POM cluster with β-CD host groups. The POM/β-CD hybrid can be dispersed in water and interacts at a water/oil interface with ligands dissolved in an oil phase through electrostatic or host-guest interactions, thereby generating POM-surfactants (POMSs) having pH, redox, and guest-competitive responsiveness, respectively. By taking advantage of the jamming of POMSs at the interface, a reconfigurable all-liquid system could be produced that is responsive to orthogonal changes in the external environment.

We present the successful fabrication of POM-based hydrogels through the host–guest interactions between the inclusion complex of Anderson–adamantane and 6-acrylamido-β-CD.