- Arundhati Deshmukh University of California, Los Angeles ,
- Niklas Geue University of California, Los Angeles & University of Manchester ,
- Nadine Bradbury University of California, Los Angeles ,
- Timothy Atallah University of California, Los Angeles & Denison University ,
- Chern Chuang University of Toronto ,
- Monica Pengshung University of California, Los Angeles ,
- Jianshu Cao Massachusetts Institute of Technology ,
- Ellen Sletten University of California, Los Angeles ,
- Daniel Neuhauser University of California, Los Angeles ,
- Justin Caram University of California, Los Angeles
Molecular aggregates with long-range excitonic couplings have drastically different photophysical properties compared to their monomer counterparts. From Kasha’s model for 1-dimensional systems, positive or negative excitonic couplings lead to blue or red shifted optical spectra with respect to the monomers, labelled H-and J-aggregates respectively. The overall excitonic couplings in higher dimensional systems are much more complicated and cannot be simply classified from their spectral shifts alone. Here, we provide a unified classification for extended 2D aggregates using temperature dependent peak shifts, thermal broadening and quantum yields. We discuss the examples of six 2D aggregates with J-like absorption spectra but quite drastic changes quantum yields and superradiance. We find the origin of the differences is, in fact, a different excitonic band structure where the bright state is lower energy than the monomer but still away from the band edge. We call this an ‘I-aggregate’. Our results provide a description of the complex excitonic behaviors that cannot be explained solely on Kasha’s model. Further, such properties can be tuned with the packing geometries within the aggregates providing supramolecular pathways for controlling them. This will allow for precise optimizations of aggregate properties in their applications across the areas of optoelectronics, photonics, excitonic energy transfer, and shortwave infrared technologies.
Major changes include (i) comparison of I-aggregates with related systems (aggregates with CT coupling, LH2 etc.), (ii) agreement between experimental and calculated red-shifts for all aggregates.