Abstract
The electronic excited states of molecular aggregates and their photophysical signatures have long fascinated spectroscopists and theoreticians alike since the advent of Frenkel exciton theory almost 90 years ago. The influence of molecular packing on basic optical probes like absorption and photoluminescence was originally worked out by Kasha for aggregates dominated by Coulombic intermolecular interactions, eventually leading to the classification of J- and H-aggregates. This review outlines advances made in understanding the relationship between aggregate structure and photophysics when vibronic coupling and intermolecular charge transfer are incorporated. An assortment of packing geometries is considered from the humble molecular dimer to more exotic structures including linear and bent aggregates, two-dimensional herringbone and "HJ" aggregates, and chiral aggregates. The interplay between long-range Coulomb coupling and short-range charge-transfer-mediated coupling strongly depends on the aggregate architecture leading to a wide array of photophysical behaviors.
Keywords
Intermolecular forceChemistryJ-aggregateChemical physicsCharge (physics)ExcitonVibronic couplingCoupling (piping)Excited statePhotoluminescenceDimerAggregate (composite)van der Waals forceNanotechnologyMoleculeAtomic physicsQuantum mechanicsPhysicsOptoelectronicsMaterials scienceOrganic chemistry
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Publication Info
- Year
- 2018
- Type
- review
- Volume
- 118
- Issue
- 15
- Pages
- 7069-7163
- Citations
- 1631
- Access
- Closed
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Cite This
Nicholas J. Hestand,
Frank C. Spano
(2018).
Expanded Theory of H- and J-Molecular Aggregates: The Effects of Vibronic Coupling and Intermolecular Charge Transfer.
Chemical Reviews
, 118
(15)
, 7069-7163.
https://doi.org/10.1021/acs.chemrev.7b00581
Identifiers
- DOI
- 10.1021/acs.chemrev.7b00581
- PMID
- 29664617