Photoinduced Electron Transfer Mechanisms in Supramolecular Systems

Photoinduced electron transfer in supramolecular systems relies on the precise assembly of electron donors and acceptors through non-covalent interactions, enabling controlled charge separation upon light excitation. Such assemblies span a broad range of architectures, from donor–acceptor dyads and triads to mechanically interlocked rotaxanes and dendritic constructs. Key driving forces include π–π stacking, electrostatic complementarity, coordination bonds and hydrogen-bond networks, each modulating the rates of charge separation and recombination. Time-resolved spectroscopies reveal ultrafast charge-separation events followed by a spectrum of lifetimes for charge-separated states, governed by spatial separation, energetic driving force and electronic coupling. Recent advances have extended lifetimes of radical ion pairs from picoseconds to milliseconds, paving the way for applications in solar energy conversion, photocatalysis and molecular electronics. The integration of carbon-based acceptors such as fullerenes or carbon nanotubes with porphyrinoid or phthalocyanine donors has proven especially fruitful, merging broad absorption profiles with efficient charge-transport pathways. Ongoing research seeks to balance light harvesting, directional electron flow and long-lived charge states, thereby approaching the efficiency and robustness of natural photosynthetic centres.

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Photoinduced Electron Transfer Mechanisms in Supramolecular Systems publication trend

The graph below shows the total number of articles in photoinduced electron transfer mechanisms in supramolecular systems across all publications each year (not limited to Nature Index journals).

Technical terms

Photoinduced electron transfer: Movement of an electron from a donor to an acceptor molecule following photoexcitation.

Charge separation: Formation of spatially distinct radical ion pairs (donor˙⁺/acceptor˙⁻) after electron transfer.

Supramolecular assembly: Organisation of molecules into structured complexes via non-covalent interactions.

π–π interactions: Stacking interactions between aromatic rings that facilitate electronic communication.

Donor–acceptor dyad/triad: Molecular construct comprising one or more electron donors covalently or non-covalently linked to an electron acceptor.

References

1. Hybrid Zn-β-Aminoporphyrin–Carbon Nanotubes: Pyrrolidine and Direct Covalent Linkage Recognition, and Multiple-Photo Response. Molecules (2023).
2. Porphyrinoid–Fullerene Hybrids as Candidates in Artificial Photosynthetic Schemes. C – Journal of Carbon Research (2019).
3. Unveiling the nature of supramolecular crown ether–C 60 interactions. Chemical Science (2015).