Enabling Ultrafast Intramolecular Singlet Fission in Perylene Diimide Tetramer with Saddle-Shaped Linker DOI
Yu Guo,

Lisi Yang,

Yixuan Gao

et al.

The Journal of Physical Chemistry Letters, Journal Year: 2024, Volume and Issue: 15(51), P. 12561 - 12570

Published: Dec. 16, 2024

Intramolecular singlet fission (SF) in multichromophore systems is of high interest for photovoltaic application. As an attractive candidate SF-based devices, enabling efficient SF covalent oligomers perylene diimide (PDI) still remains challenging. In this work, inter-PDI with τSF = ∼150 ps and ∼150% triplet yield a tetramer COTh-FPDI was facilitated by employing saddle-shaped cyclooctatetrathiophene (COTh) core fused linking PDIs. comparison, ultrafast symmetry-breaking charge separation (τCS ∼100 fs) observed the COTh-αPDI flexible linking. Taking advantage rigid minimized excited-state structural relaxation, unique geometry can be fully defined topological characteristic COTh, which plays key role electronic coupling required SF. Our work provides new strategy intramolecular predefining interchromophore structure, might inspired future designing systems.

Language: Английский

Resolving the Vibronic Effect on Dark Processes of Conjugation Extended Diketopyrrolopyrrole with Red/NIR Emitting DOI
Zilong Guo, Pengcai Liu, Yulin Sha

et al.

The Journal of Physical Chemistry Letters, Journal Year: 2025, Volume and Issue: unknown, P. 4615 - 4625

Published: May 1, 2025

The conjugation extended emitters with bright red/NIR emission are of high interest due to potential bioapplications, while they might be plagued from fluorescence quenching associated the rapid dark decay channels excited states. In this work, we employed diketopyrrolopyrrole (DPP) and derivatives as a model system attempted resolve excited-state dynamics by using ultrafast spectroscopy. Further vibrational analysis on electronic states (S0, S1, T1, T2) allowed us evaluate vibronic effects processes system, including S1 state nonradiative (kNRS) plausible ISC (kISC) channels. By identification modes involved in corresponding processes, relationship between structure relaxation, coupling, rate constant was revealed. Our work indicated that effect can greatly affect fluorescent promoting should taken into consideration molecular design emitters.

Language: Английский

Citations

0
Enabling Ultrafast Intramolecular Singlet Fission in Perylene Diimide Tetramer with Saddle-Shaped Linker DOI
Yu Guo,

Lisi Yang,

Yixuan Gao

et al.

The Journal of Physical Chemistry Letters, Journal Year: 2024, Volume and Issue: 15(51), P. 12561 - 12570

Published: Dec. 16, 2024

Intramolecular singlet fission (SF) in multichromophore systems is of high interest for photovoltaic application. As an attractive candidate SF-based devices, enabling efficient SF covalent oligomers perylene diimide (PDI) still remains challenging. In this work, inter-PDI with τSF = ∼150 ps and ∼150% triplet yield a tetramer COTh-FPDI was facilitated by employing saddle-shaped cyclooctatetrathiophene (COTh) core fused linking PDIs. comparison, ultrafast symmetry-breaking charge separation (τCS ∼100 fs) observed the COTh-αPDI flexible linking. Taking advantage rigid minimized excited-state structural relaxation, unique geometry can be fully defined topological characteristic COTh, which plays key role electronic coupling required SF. Our work provides new strategy intramolecular predefining interchromophore structure, might inspired future designing systems.

Language: Английский

Citations

0