Fully Conjugated Porphyrin Glass: Collective Light-Harvesting Antenna for Near-Infrared Fluorescence beyond 1 μm

ACS Omega. 2018 Apr 30;3(4):4466-4474. doi: 10.1021/acsomega.8b00566. Epub 2018 Apr 24.

Abstract

Expanded π-systems with a narrow highest occupied molecular orbital-lowest unoccupied molecular orbital band gap encounter deactivation of excitons due to the "energy gap law" and undesired aggregation. This dilemma generally thwarts the near-infrared (NIR) luminescence of organic π-systems. A sophisticated cofacially stacked π-system is known to involve exponentially tailed disorder, which displays exceptionally red-shifted fluorescence even as only a marginal emission component. Enhancement of the tail-state fluorescence might be advantageous to achieve NIR photoluminescence with an expected collective light-harvesting antenna effect as follows: (i) efficient light-harvesting capacity due to intense electronic absorption, (ii) a long-distance exciton migration into the tail state based on a high spatial density of the chromophore site, and (iii) substantial transmission of NIR emission to circumvent the inner filter effect. Suppression of aggregation-induced quenching of fluorescence could realize collective light-harvesting antenna for NIR-luminescence materials. This study discloses an enhanced tail-state NIR fluorescence of a self-standing porphyrin film at 1138 nm with a moderate quantum efficiency based on a fully π-conjugated porphyrin that adopts an amorphous form, called "porphyrin glass".