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

Long-Lived Intramolecular Charge Transfer in Persubstituted Perylenediimide DOI
Anjana V. Muralidharan, Kavya Vinod, Fathima Thasnim Pattanmarthodiyil

et al.

The Journal of Physical Chemistry C, Journal Year: 2025, Volume and Issue: unknown

Published: March 3, 2025

Photoinduced charge transfer (CT) states play a pivotal role in increasing the power conversion efficiency of molecular systems used artificial photosynthesis, photocatalysis, and optronic devices. The absence intrinsic CT is one main reasons for poor photoconversion efficiencies organic chromophores like perylenediimide (PDI). Herein, we explore excited state dynamics persubstituted PDI (AP) with amino groups at ortho positions bromine atoms bay positions. Due to influence on core, nonradiative pathways are accessed photoexcitation AP. Femtosecond nanosecond transient absorption measurements weakly polar solvents showed relaxation higher singlet picoseconds time scale, paving way an intramolecular (ICT) having lifetime nanoseconds scale. As dielectric medium changed from solvent (toluene, ε = 2.38) (ethyl acetate, 6.02), stabilized decreased τ 69.1 ± 1.7 ns 47.1 0.5 ns, which confirms dependency ICT state. Theoretical investigations employing surface hopping suggest that rate internal (kIC 1.13 × 1011 s–1) competes intersystem crossing (kISC 0.85 Amination position induces characteristics core PDI, as evident hole–electron analysis S1 Presented results long-lived relaxed may improve designing strategies optoelectronic

Language: Английский

Citations

0
Core-Twist Modulated Intersystem Crossing in a π-Fused Single-Molecule DOI
Aniruddha Mazumder, Pallavi Panthakkal Das, Kavya Vinod

et al.

The Journal of Physical Chemistry Letters, Journal Year: 2025, Volume and Issue: unknown, P. 4643 - 4651

Published: May 2, 2025

Herein, we present direct evidence of intersystem crossing (ISC) in a core-twisted naphthalenemonoimide-fused perylenediimide (NP) at the single-molecule level. The ISC process was characterized by frequent quantum jumps (short off states) fluorescence measurements. singlet to triplet NP corroborated ultrafast transient absorption exhibits with rate constant kISC = 6.5 × 107 s-1 and yield ϕT 25.8 ± 2.4%. Our theoretical investigations unveil potential state mixing between first excited S1 third T3, thus providing insight into mechanism during relaxation from Franck-Condon region its optimal geometry state. current investigation provides critical insights twist-induced polyaromatic hydrocarbon both ensemble levels.

Language: Английский

Citations

0
A Light-Responsive Metal–Organic Framework with Perchlorinated Nanographene Ligands DOI
Xin Zheng, Nikita Gupta, Haiying He

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: May 4, 2025

Harnessing water as a sustainable electron source for artificial photosynthesis remains significant challenge. This work presents Alice-MOF-1, novel zirconium metal-organic framework (MOF) incorporating hexatopic ligands with perchlorinated hexa-peri-hexabenzocoronene (HBC) core, photocatalyst CO2 reduction using the terminal donor. Contortion of ligand, induced by edge chlorination, minimizes π-stacking and enhances solubility, enabling direct MOF synthesis. The controlled arrangement chromophores within Alice-MOF-1 is crucial complex multielectron redox reactions. unique ligand architecture promotes symmetry-breaking charge transfer (SBCT), mechanism observed in natural photosynthesis, leading to efficient separation minimal energy loss. Femtosecond transient absorption spectroscopy time-resolved paramagnetic resonance (EPR) confirm formation long-lived radical ions, providing evidence SBCT negligible recombination. These findings demonstrate power MOF-based chromophore assemblies mimic nature's light-harvesting strategies conversion.

Language: Английский

Citations

0
Accelerating Symmetry-Breaking Charge Separation in an Angular versus Linear Perylenediimide Dimer through the Modulation of Coulombic Coupling DOI
Aniruddha Mazumder, Kavya Vinod,

Anil Thomas

et al.

The Journal of Physical Chemistry Letters, Journal Year: 2025, Volume and Issue: unknown, P. 4819 - 4827

Published: May 8, 2025

Achieving faster charge separation in organic systems capable of mimicking the electron transfer events natural photosynthesis has been an exciting research topic for several decades. Herein, we demonstrate orientation-dependent acceleration symmetry-breaking (SB-CS) angular (A-PDI2) versus linear (L-PDI2) perylenediimide dimer. Femtosecond transient absorption measurements reveal ultrafast SB-CS A-PDI2 (τCS = 6.3 ps) with ∼20 times than L-PDI2 127.9 ps). Nanosecond establish negligible population triplet excited-states (ϕT < 1%), whereas a significant excited-state 35.9%) is quantified A-PDI2. The theoretically computed Coulombic coupling strength (|JCoul| 14.9 cm-1) and 438.4 rationalized as crucial factor modulating rates. current investigation could be beneficial designing light harvesting materials efficient optoelectronic devices.

Language: Английский

Citations

0
Single-Molecule Detection of a Terrylenediimide-Based Near-Infrared Emitter DOI Creative Commons

Suvarna Sujilkumar,

Philip Daniel Maret, Kavya Vinod

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

Design and single-molecule level scrutiny of a novel NIR absorbing emitting terrylenediimide-based chromophore, TDI-TPA 4 , is reported. The energy gap law dielectric dependence are validated at ensemble domains.

Language: Английский

Citations

0
Mono- and Bichromophores Formed from Perylene Monoimide Diesters: Competition between Intramolecular Charge Transfer and Intermolecular Singlet Exciton Fission DOI Creative Commons
Demet Demirci Gültekin, Serkan Şen, Ayhan Elmalı

et al.

The Journal of Physical Chemistry A, Journal Year: 2024, Volume and Issue: 128(44), P. 9614 - 9626

Published: Oct. 23, 2024

Perylene monoimide diesters and the corresponding phenyl-linked bichromophores are strongly fluorescent in dilute solution with minimal triplet population after relaxation of initial Franck-Condon state. The monomer forms nonemissive face-to-face dimers solution, wherein illumination leads to formation a spin-correlated, pair yield

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