Self-Assembly-Directed Exciton Diffusion in Solution-Processable Metalloporphyrin Thin Films

The study of excited-state energy diffusion has had an important impact in the development and optimization of organic electronics. For instance, optimizing excited-state energy migration in the photoactive layer in an organic solar cell device has been shown to yield efficient solar energy conversion. Despite the crucial role that energy migration plays in molecular electronic device physics, there is still a great deal to be explored to establish how molecular orientation impacts energy diffusion mechanisms. In this work, we have synthesized a new library of solution-processable, Zn (alkoxycarbonyl)phenylporphyrins containing butyl (ZnTCB4PP), hexyl (ZnTCH4PP), 2-ethylhexyl (ZnTCEH4PP), and octyl (ZnTCO4PP) alkoxycarbonyl groups. We establish that, by varying the length of the peripheral alkyl chains on the metalloporphyrin macrocycle, preferential orientation and molecular self-assembly is observed in solution-processed thin films. The resultant arrangement of molecules consequently affects the electronic and photophysical characteristics of the metalloporphyrin thin films. The various molecular arrangements in the porphyrin thin films and their resultant impact were determined using UV-Vis absorption spectroscopy, steady-state and time-resolved fluorescence emission lifetimes, and X-ray diffraction in thin films. The films were doped with C60 quencher molecules and the change in fluorescence was measured to derive a relative quenching efficiency. Using emission decay, relative quenching efficiency, and dopant volume fraction as input, insights on exciton diffusion coefficient and exciton diffusion lengths were obtained from a Monte Carlo simulation. The octyl derivative (ZnTCO4PP) showed the strongest relative fluorescence quenching and, therefore, the highest exciton diffusion coefficient (5.29 × 10−3 cm2 s−1) and longest exciton diffusion length (~81 nm). The octyl derivative also showed the strongest out-of-plane stacking among the metalloporphyrins studied. This work demonstrates how molecular self-assembly can be used to modulate and direct exciton diffusion in solution-processable metalloporphyrin thin films engineered for optoelectronic and photonic applications.

Cyclometalated Iridium-Coumarin Ratiometric Oxygen Sensors: Improved Signal Resolution and Tunable Dynamic Ranges

In this work we introduce a new series of ratiometric oxygen sensors for hypoxic environments based on phosphorescent cyclometalated iridium centers partnered with organic coumarin fluorophores. Three different cyclometalating ligands and two different pyridyl-containing coumarin types were used to prepare six target complexes with tunable excited-state energies. Some of the complexes exhibit only phosphorescence originating from the cyclometalated Ir moiety, as a result of excited-state energy transfer from the coumarin to the Ir-centered excited states. Three of the complexes display dual emission, with fluorescence arising from the coumarin ligands and phosphorescence from the cyclometalated iridium synthons, and hence function as ratiometric oxygen sensors. Oxygen quenching experiments with these complexes demonstrate that the iridium centered phosphorescence is quenched under O₂ while fluorescence is unaffected. These sensors have good signal resolution, and the sensitivity and dynamic range, measured with Stern-Volmer analysis, span two orders of magnitude. This work demonstrates that this simple, modular approach for conjoining fluorescent and phosphorescent molecules can produce effective oxygen sensors with a wide range of attributes.

Cyclometalated Iridium-Coumarin Ratiometric Oxygen Sensors: Improved Signal Resolution and Tunable Dynamic Ranges

In this work we introduce a new series of ratiometric oxygen sensors for hypoxic environments based on phosphorescent cyclometalated iridium centers partnered with organic coumarin fluorophores. Three different cyclometalating ligands and two different pyridyl-containing coumarin types were used to prepare six target complexes with tunable excited-state energies. Some of the complexes exhibit only phosphorescence originating from the cyclometalated Ir moiety, as a result of excited-state energy transfer from the coumarin to the Ir-centered excited states. Three of the complexes display dual emission, with fluorescence arising from the coumarin ligands and phosphorescence from the cyclometalated iridium synthons, and hence function as ratiometric oxygen sensors. Oxygen quenching experiments on these complexes demonstrate that the iridium centered phosphorescence is quenched under O₂ while fluorescence is unaffected. These sensors have good signal resolution, and the sensitivity and dynamic range, measured with Stern-Volmer analysis, span two orders of magnitude. This work demonstrates that this simple, modular approach for conjoining fluorescent and phosphorescent molecules can produce effective oxygen sensors with a wide range of attributes.