Solution Shearing of Zirconium (Zr)-Based Metal-Organic Frameworks NU-901 and MOF-525 Thin Films for Electrocatalytic Reduction Applications.

Solution shearing, a meniscus-guided coating process, can create large-area metal-organic framework (MOF) thin films rapidly, which can lead to the formation of uniform membranes for separations or thin films for sensing and catalysis applications. Although previous work has shown that solution shearing can render MOF thin films, examples have been limited to a few prototypical systems, such as HKUST-1, Cu-HHTP, and UiO-66. Here, we expand on the applicability of solution shearing by making thin films of NU-901, a zirconium-based MOF. We study how the NU-901 thin film properties (i.e., crystallinity, surface coverage, and thickness) can be controlled as a function of substrate temperature and linker concentration. High fractional surface coverage of small-area (∼1 cm2) NU-901 thin films (0.88 ± 0.06) is achieved on a glass substrate for all conditions after one blade pass, while a low to moderate fractional surface coverage (0.73 ± 0.18) is obtained for large-area (∼5 cm2) NU-901 thin films. The crystallinity of NU-901 crystals increases with temperature and decreases with linker concentration. On the other hand, the adjusted thickness of NU-901 thin films increases with both increasing temperature and linker concentration. We also extend the solution shearing technique to synthesize MOF-525 thin films on a transparent conductive oxide that are useful for electrocatalysis. We show that Fe-metalated MOF-525 films can reduce CO2 to CO, which has implications for CO2 capture and utilization. The demonstration of thin film formation of NU-901 and MOF-525 using solution shearing on a wide range of substrates will be highly useful for implementing these MOFs in sensing and catalytic applications.

The Tungsten-Promoted Synthesis of Piperidyl-Modified erythro-Methylphenidate Derivatives.

Due to its efficacy as a dopamine receptor agonist, methylphenidate (MPH) is of interest as a potential therapeutic for cocaine addiction. While numerous derivatives of MPH have been investigated for their potential medicinal value, functionalization of the piperidine ring has not been explored. The pyridine borane ligand in WTp(NO)(PMe3)(η2-pyBH3) is dearomatized by the metal and can be elaborated to the analogous η2-mesylpyridinium complex. Installing a methyl phenylacetate moiety at the C2' position via a Reformatsky reaction followed by a tandem protonation/nucleophilic addition sequence results in a library of erythro MPH analogues functionalized at the piperidyl C5' position. The functional group is added chemoselectively to C5', cis to the methyl phenylacetate. Repeating this procedure with an enantioenriched source of the tungsten reagent results in enantioenriched MPH derivatives. All identities of the newly reported compounds are supported by comprehensive 2D NMR and HRMS data or crystallographic data.

A novel reactive processing technique: using telechelic polymers to reactively compatibilize polymer blends.

Difunctional reactive polymers, telechelics, were used to reactively form multiblock copolymers in situ when melt-blended with a blend of polystyrene and polyisoprene. To quantify the ability of the copolymer to compatibilize the blends, the time evolution of the domain size upon annealing was analyzed by SEM. It was found that the most effective parameter to quantify the ability of the copolymer to inhibit droplet coalescence is K(rel)t(stable), the relative coarsening constant multiplied by the stabilization time. These results indicate that intermediate-molecular-weight telechelic pairs of both highly reactive Anhydride-PS-Anhydride/NH(2)-PI-NH(2) and slower reacting Epoxy-PS-Epoxy/COOH-PI-COOH both effectively suppress coalescence, with the optimal molecular weight being slightly above the critical molecular weight of the homopolymer, M(c). The effects of telechelic loading were also investigated, where the optimal loading concentration for this system was 0.5 wt %, as higher concentrations exhibited a plasticizing effect due to the presence of unreacted low-molecular-weight telechelics present in the blend. A determination of the interfacial coverage of the copolymer shows that a conversion of approximately 1.5-3.0% was required for 20% surface coverage at 5.0 wt % telechelic loading, indicating a large excess of telechelics in this system. At the optimal loading level of 0.5 wt %, a conversion of 15% was required for 20% surface coverage. The results of these experiments provide a clear understanding of the role of telechelic loading and molecular weight on its ability to reactively form interfacial modifiers in phase-separated polymer blends and provide guidelines for the development of similar reactive processing schemes that can use telechelic polymers to reactively compatibilize a broad range of polymer blends.