A Decoupled-Motif Strategy Directs Supramolecular Charge-Transfer Architectures Toward Efficient Photocatalytic H₂...

Area of Science:

• Supramolecular chemistry
• Photochemistry
• Materials science

Background:

• Supramolecular topology significantly influences the behavior of charge-transfer (CT) excitons in donor-acceptor systems.
• Controlling exciton pathways is crucial for developing advanced photochemical applications.

Purpose of the Study:

• To investigate how tailoring the geometric connectivity of NDI-pyrene conjugates (NPCs) affects CT exciton dynamics.
• To establish a link between supramolecular assembly, topology, and photocatalytic function.

Main Methods:

• Synthesis of NDI-pyrene conjugates (NPCs) with varying geometric connectivities.
• Comprehensive structural characterization.
• Detailed photophysical analyses, including steady-state and time-resolved spectroscopy.

Main Results:

• Confined topologies were found to localize electron-hole pairs, forming emissive CT states.
• Segregated double-cable architectures facilitated long-range charge migration.
• Visible-light-driven H2 evolution was achieved using segregated architectures.

Conclusions:

• Geometric confinement is a key design principle for controlling excited-state dynamics in supramolecular assemblies.
• Topology dictates whether CT excitons lead to emissive states or efficient photocatalysis.
• This work provides a framework for designing supramolecular materials for targeted photochemical outcomes, such as hydrogen production.