  Soft particles such as microgels and core-shell particles can undergo
significant and anisotropic deformations when adsorbed to a liquid interface.
This, in turn, leads to a complex phase behavior upon compression. Here we
develop a multiscale framework to rationally link the molecular particle
architecture to the resulting interfacial morphology and, ultimately, to the
collective interfacial phase behavior, enabling us to identify the key
single-particle properties underlying two-dimensional continuous,
heterostructural, and isostructural solid-solid transitions. Our approach
resolves existing discrepancies between experiments and simulations and thus
provides a unifying framework to describe phase transitions in interfacial
soft-particle systems. We establish proof-of-principle for our rational
approach by synthesizing three different poly(N-isopropylacrylamide)
soft-particle architectures, each of which corresponds to a different targeted
phase behavior. In parallel, we introduce a versatile and highly efficient
coarse-grained simulation method that adequately captures the qualitative key
features of each soft-particle system; the novel ingredient in our simulation
model is the use of auxiliary degrees of freedom to explicitly account for the
swelling and collapse of the particles as a function of surface pressure.
Notably, these combined efforts allow us to establish the first experimental
demonstration of a heterostructural transition to a chain phase in a
single-component system, as well as the first accurate in silico account of the
two-dimensional isostructural transition. Overall, our multiscale framework
provides a bridge between physicochemical soft-particle characteristics at the
molecular- and nanoscale and the collective self-assembly phenomenology at the
macroscale, paving the way towards novel materials with on-demand interfacial
behavior.
