Solid-State Nuclear Magnetic Resonance Techniques for the Structural Characterization of Geminal Alane-Phosphane Frustrated Lewis Pairs and Secondary Adducts

Macroscopic materials with nanoscopic properties have recently been synthesized by self-assembling defined nanoparticles to form self-supported networks, so-called aerogels. Motivated by the promising properties of this class of materials, the search for versatile routes toward the controlled assembly of presynthesized nanoparticles into such ultralight macroscopic materials has become a great interest. Overcoating procedures of colloidal nanoparticles with polymers offer versatile means to produce aerogels from nanoparticles, regardless of their size, shape, or properties while retaining their original characteristics. Herein, we report on the surface modification and assembly of various building blocks: photoluminescent nanorods, magnetic nanospheres, and plasmonic nanocubes with particle sizes between 5 and 40 nm. The polymer employed for the coating was poly(isobutylene-alt-maleic anhydride) modified with 1-dodecylamine side chains. The amphiphilic character of the polymer facilitates the stability of the nanocrystals in aqueous media. Hydrogels are prepared via triggering the colloidally stable solutions, with aqueous cations acting as linkers between the functional groups of the polymer shell. Upon supercritical drying, the hydrogels are successfully converted into macroscopic aerogels with highly porous, open structure. Due to the noninvasive preparation method, the nanoscopic properties of the building blocks are retained in the monolithic aerogels, leading to the powerful transfer of these properties to the macroscale. The open pore system, the universality of the polymer-coating strategy, and the large accessibility of the network make these gel structures promising biosensing platforms. Functionalizing the polymer shell with biomolecules opens up the possibility to utilize the nanoscopic properties of the building blocks in fluorescent probing, magnetoresistive sensing, and plasmonic-driven thermal sensing.

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Recommended citation: Anna-Lena Wübker, Jonas Koppe, Henrik Bradtmüller, Lukas Keweloh, Damian Pleschka, Werner Uhl, Michael Ryan Hansen, Hellmut Eckert, Chem Eur. J. 2021, 27, 13249-13257.