Exciton Delocalization Counteracts the Energy Gap: A New Pathway toward NIR-Emissive Dyes

• Exciton coupling between the transition dipole moments of ordered dyes in supramolecular assemblies, so-called J/H-aggregates, leads to shifted electronic transitions. This can lower the excited state energy, allowing for emission well into the near-infrared regime. However, as we show here, it is not only the excited state energy modifications that J-aggregates can provide. A bay-alkylated quaterrylene was synthesized, which was found to form J-aggregates in 1,1,2,2-tetrachloroethane. A combination of superradiance and a decreased nonradiative relaxation rate made the J-aggregate four times more emissive than the monomeric counterpart. A reduced nonradiative relaxation rate is a nonintuitive consequence following the 180 nm (3300 cm(-1)) red-shift of the J-aggregate in comparison to the monomeric absorption. However, the energy gap law, which is commonly invoked to rationalize increased nonradiative relaxation rates with increasing emission wavelength, also contains a reorganization energy term. The reorganization energy is highly suppressed in J-aggregates due to exciton delocalization, and the framework of the energy gap law could therefore reproduce our experimental observations. J-Aggregates can thus circumvent the common belief that lowering the excited state energies results in large nonradiative relaxation rates and are thus a pathway toward highly emissive organic dyes in the NIR regime.

Ämnesord

MEDICIN OCH HÄLSOVETENSKAP  -- Medicinska och farmaceutiska grundvetenskaper -- Andra medicinska och farmaceutiska grundvetenskaper (hsv//swe)

MEDICAL AND HEALTH SCIENCES  -- Basic Medicine -- Other Basic Medicine (hsv//eng)

NATURVETENSKAP  -- Kemi -- Fysikalisk kemi (hsv//swe)

NATURAL SCIENCES  -- Chemical Sciences -- Physical Chemistry (hsv//eng)

NATURVETENSKAP  -- Kemi (hsv//swe)

NATURAL SCIENCES  -- Chemical Sciences (hsv//eng)

Nyckelord

j-aggregate

enhancement

bodipy

Chemistry

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