# Function from Confinement: Ligand-Coated Nanoparticles as Functional Materials

## TL;DR

This paper reviews how ligand-coated nanoparticles can be designed to perform complex functions by leveraging the properties of their organic surface layers.

## Contribution

The paper introduces a systems-chemistry perspective to understand and design functional nanomaterials with active organic layers.

## Key findings

- Ligand-coated nanoparticles exhibit emergent properties due to nanoconfinement and collective interactions.
- The organic layer can drive functions like catalysis, sensing, and programmable assembly.
- Design principles for hybrid organic–inorganic nanosystems are proposed based on chemical constitution.

## Abstract

For nanoparticles stabilized by self-assembled monolayers,
the
surface-bound molecular species not only modify the core material
properties but also provide a handle for interaction with other components,
whether they are molecular, nanoscale, or even macroscopic. Importantly,
when confined to nanosurfaces, these organic entities exhibit emergent
properties that impart unique functionalities to the underlying nanomaterial.
In this Review, we examine how these capabilities originate from the
structural organization and collective interactions within on-nanoparticle
self-assembled monolayers, drawing on examples of quasi-spherical
nanoparticles smaller than ca. 8 nm in size. Our focus spans four
key categories of function: (i) catalysis and chemical transformation
under nanoconfinement, (ii) molecular recognition and sensing, (iii)
switching and adaptation, and (iv) programmable nanoparticle assembly.
By adopting a systems-chemistry perspective to identify how function
is defined by chemical constitution, we elucidate design principles
and strategies that we envisage can be broadly applied to a variety
of hybrid organic–inorganic nanosystems. We also highlight
the current challenges and future opportunities in the field of functional
nanoparticles stabilized by self-assembled monolayers. Our aim is
to motivate the community to shift toward a perspective in which the
organic layer is understood as an active driver of the system functionality
rather than a passive component. By harnessing its dynamic and adaptative
nature, researchers can design functionally sophisticated and chemically
programmable nanomaterials, unlocking unexplored possibilities in
active materials, nanocatalysis, molecular recognition, sensing, and
delivery.