nn2c00266_si_001.pdf (24.27 MB)
Hybrid Nanocrystals of Small Molecules and Chemically Disordered Polymers
journal contribution
posted on 2022-05-19, 16:11 authored by Eric P. Bruckner, Tine Curk, Luka Đorđević, Ziwei Wang, Yang Yang, Ruomeng Qiu, Adam J. Dannenhoffer, Hiroaki Sai, Jacob Kupferberg, Liam C. Palmer, Erik Luijten, Samuel I. StuppOrganic
crystals formed by small molecules can be highly functional
but are often brittle or insoluble structures with limited possibilities
for use or processing from a liquid phase. A possible solution is
the nanoscale integration of polymers into organic crystals without
sacrificing long-range order and therefore function. This enables
the organic crystals to benefit from the advantageous mechanical and
chemical properties of the polymeric component. We report here on
a strategy in which small molecules cocrystallize with side chains
of chemically disordered polymers to create hybrid nanostructures
containing a highly ordered lattice. Synchrotron X-ray scattering,
absorption spectroscopy, and coarse-grained molecular dynamics simulations
reveal that the polymer backbones form an “exo-crystalline”
layer of disordered chains that wrap around the nanostructures, becoming
a handle for interesting properties. The morphology of this “hybrid
bonding polymer” nanostructure is dictated by the competition
between the polymers’ entropy and the enthalpy of the lattice
allowing for control over the aspect ratio of the nanocrystal by changing
the degree of polymer integration. We observed that nanostructures
with an exo-crystalline layer of polymer exhibit enhanced fracture
strength, self-healing capacity, and dispersion in water, which benefits
their use as light-harvesting assemblies in photocatalysis. Guided
by computation, future work could further explore these hybrid nanostructures
as components for functional materials.
History
Usage metrics
Categories
Keywords
future work couldpolymer backbones formpolymers ’ entropysmall molecules cocrystallizehighly ordered latticecrystalline ” layerchemically disordered polymerssmall moleculescrystalline layerpolymer integrationlattice allowinghighly functionaldisordered chainswrap aroundtherefore functionsynchrotron xside chainsray scatteringrange orderpossible solutionpolymeric componentorganic crystalsoften brittlenanoscale integrationliquid phaselimited possibilitiesinteresting propertiesinsoluble structureshybrid nanocrystalshealing capacityharvesting assembliesfunctional materialschemical propertiesaspect ratioadvantageous mechanicalabsorption spectroscopy