# Beyond Cocrystals: Hierarchical Functional Assemblies via Noncovalent Synthesis

## TL;DR

This review explores how non-covalent interactions can be used to build complex organic structures with potential optoelectronic applications.

## Contribution

The paper introduces strategies for constructing hierarchical organic structures using cocrystals as building blocks.

## Key findings

- Sequential nucleation of cocrystals can lead to complex hierarchical structures.
- Non-covalent interactions significantly influence the physicochemical properties of cocrystals.
- Applications of these structures in optoelectronics are promising but require further development.

## Abstract

Cocrystals are solid crystals formed by the combination of multiple components through non‐covalent interactions (NCIs). Despite their diverse structures and tunable optoelectronic properties, they cannot meet the demand for multi‐functionalization of optoelectronic devices. Therefore, a series of strategies is summarized to construct organic hierarchical structures (OHSs) by self‐assembly of NCIs using organic cocrystals as base building blocks. Sequential nucleation of cocrystals has been achieved by regulating the strength of NCIs to further synthesize complex OHSs. This review explores the fundamental factors affecting the physicochemical properties of cocrystals, such as molecular arrangement, the distance and orientation of intermolecular interactions, etc. Additionally, the self‐assembly process of synthetic OHSs driven by single & multiple NCIs is analyzed, along with the applications of these structures in optoelectronics. Finally, urgent issues on preparing OHSs are raised, and an outlook on possible future opportunities is provided.

Non‐covalent interactions (NCIs) drive the formation of organic cocrystals with diverse structures and tunable optoelectronic properties. This review explores the essential factors governing these properties, highlighting how the sequential nucleation of cocrystals leads to the self‐assembly of organic hierarchical structures (OHSs). Finally, various application‐oriented structures are presented, and challenges in preparing OHSs are discussed.