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revised on 17.05.2019, 23:23 and posted on 20.05.2019, 16:49by Arundhati Deshmukh, Danielle Koppel, Chern Chuang, Danielle Cadena, Jianshu Cao, Justin Caram
which utilize near-infrared (700 – 1000 nm) and short-wave infrared (1000 –
2000 nm) electromagnetic radiation have applications in deep-tissue imaging,
telecommunications and satellite telemetry due to low scattering and decreased
background signal in this spectral region. It is therefore necessary to develop
materials that absorb light efficiently beyond 1000 nm. Transition dipole
moment coupling (e.g. J-aggregation) allows for redshifted excitonic states and
provides a pathway to highly absorptive electronic states in the infrared. We present aggregates of two cyanine dyes whose
absorption peaks redshift dramatically upon aggregation in water from ~800
nm to 1000 nm and 1050 nm respectively with sheet-like morphologies and high
molar absorptivities (e ~ 105 M-1cm-1). We use Frenkel exciton theory to extend
Kasha’s model for J and H aggregation and describe the excitonic states of
2-dimensional aggregates whose slip is controlled by steric hindrance in the
assembled structure. A consequence of the increased dimensionality is the
phenomenon of an intermediate “I-aggregate”, one which redshifts yet displays
spectral signatures of band-edge dark states akin to an H-aggregate. We
distinguish between H-, I- and J-aggregates by showing the relative position of
the bright (absorptive) state within the density of states using temperature
dependent spectroscopy. I-aggregates hold potential for applications as charge
injection moieties for semiconductors and donors for energy transfer in NIR and
SWIR. Our results can be used to better design chromophores with predictable
and tunable aggregation with new photophysical properties.