A new catalytic transformation of saturated hydrocarbons involving carboncarbon bond cleavage and alumination is developed and investigated for the upcycling conversion of polyolefins into biodegradable fatty alcohols and fatty acids.
The immobilization of molecularly
precise metal complexes to substrates,
such as silica, provides an attractive platform for the design of
active sites in heterogeneous catalysts. Specific steric and electronic
variations of the ligand environment enable the development of structure–activity
relationships and the knowledge-driven design of catalysts. At present,
however, the three-dimensional environment of the precatalyst, much
less the active site, is generally not known for heterogeneous single-site
catalysts. We explored the degree to which NMR-based surface-to-complex
interatomic distances could be used to solve the three-dimensional
structures of three silica-supported metal complexes. The structure
solution revealed unexpected features related to the environment around
the metal that would be difficult to discern otherwise. This approach
appears to be highly robust and, due to its simplicity, is readily
applied to most single-site catalysts with little extra effort.
The library of imine-linked covalent organic frameworks
(COFs)
has grown significantly over the last two decades, featuring a variety
of morphologies, pore sizes, and applications. An array of synthetic
methods has been developed to expand the scope of the COF functionalities;
however, most of these methods were designed to introduce functional
scaffolds tailored to a specific application. Having a general approach
to diversify COFs via late-stage incorporation of functional group
handles would greatly facilitate the transformation of these materials
into platforms for a variety of useful applications. Herein, we report
a general strategy to introduce functional group handles in COFs via
the Ugi multicomponent reaction. To demonstrate the versatility of
this approach, we have synthesized two COFs with hexagonal and kagome
morphologies. We then introduced azide, alkyne, and vinyl functional
groups, which could be readily utilized for a variety of post-synthetic
modifications. This facile approach enables the functionalization
of any COFs containing imine linkages.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.