An Improved Method for Site‐Specific End Modification of Zeolite L for the Formation of Zeolite L and Gold Nanoparticle Self‐Assembled Structures

The ability to site‐selectively modify micro‐ and nanosized particles has allowed for directed self‐assembly in two and three dimensions. Site‐selective modification of particles can be a complicated task requiring the pre‐organization of particles or enhanced particle fabrication methods. The aluminum silicate, zeolite L has been reported to undergo site‐specific modification at the zeolite channel entrances, post‐fabrication in a solution‐based method. The process by which the channel entrances are site selectively modified is explored here. The preliminary step of charging the zeolite channels with aqueous acid allows for catalysis of covalent bond formation at the channel entrances. Three new end‐specific modification reagents are described based on silanol and silyl ether functional groups. These reagents are purified by column chromatography and characterized by¹H NMR spectroscopy and high resolution mass spectrometry (HRMS); they provide for reliable end modification of zeolites L. Preferential reactivity at the channel entrances is also observed. The utility of the approach is demonstrated by modifying zeolite L with adamantane at the channel entrances. Site‐specific self‐assembly with β‐cyclodextrin coated gold nanoparticles can be triggered with a chemical stimulus. The resulting multivalent host‐guest interactions give gold clustered nanoparticles at the ends of the micrometer‐sized zeolites.