Twist Angle Plays an Important Role in Photophysical Properties of a Donor–Acceptor-Type Conjugated Polymer: A Combined Ensemble and Single-Molecule Study
Abstract
We investigated photophysical properties of a donor-acceptor-type conjugated polymer by means of ensemble and single-molecule spectroscopy as well as density functional theory (DFT) calculation. The polymer is based on an alkyne-linked 1,8-carbazole (Cz) and possesses a benzothiadiazole (BT) as an electron acceptor moiety. A comparison with model compounds demonstrated that the dimer structure is the spectroscopic unit of the polymer. Single-molecule two-color excitation fluorescence and fluorescence lifetime experiments showed that the polymer molecules displayed broad distributions of fluorescence intensity ratio and fluorescence lifetime. Together with the DFT calculation, we demonstrated that the twist angle between the Cz and BT moieties played a central role in deciding those spectroscopic properties of the polymer. This result was further supported by single-molecule fluorescence spectral measurement. The spectral measurement also suggested intersegment interactions within the single chains. Furthermore, single-molecule defocused and polarization fluorescence imaging suggested efficient exciton migration and trapping occurring within the single polymer chain. These experiments also revealed changes of the lowest energy site within the single polymer molecules.
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A twist between monomers on donor-acceptor-type CPs has a large effect on their fluorescence characteristics.
“In addition, a twist between monomers on donor–acceptor-type CPs has a large effect on their fluorescence characteristics.150,164”
From The Pursuit of Shortwave Infrared-Emitting Nanoparticles with Bright Fluorescence through Molecular Design and Excited-State Engineering of Molecular Aggregates (2022) · cites this paper as [150]
The excited TICT state might be suppressed by an inhibition of conformational rotation either by embedding the molecule into a rigid matrix or by the formation of a densely packed aggregated state of the molecule.
“The excited TICT state might be suppressed by an inhibition of conformational rotation either by embedding the molecule into a rigid matrix150 or by the formation of a densely packed aggregated state of the molecule.109”
From The Pursuit of Shortwave Infrared-Emitting Nanoparticles with Bright Fluorescence through Molecular Design and Excited-State Engineering of Molecular Aggregates (2022) · cites this paper as [150]
A twist between monomers on donor-acceptor-type CPs has a large effect on their fluorescence characteristics.
“In addition, a twist between monomers on donor–acceptor-type CPs has a large effect on their fluorescence characteristics.150,164”
From The Pursuit of Shortwave Infrared-Emitting Nanoparticles with Bright Fluorescence through Molecular Design and Excited-State Engineering of Molecular Aggregates (2022) · cites this paper as [164]
A single-molecule photophysical study of the D-A-type conjugated polymer CzBT revealed unique intersegment interactions and a whole-chain conformation that depend on the twist angle between donor and acceptor.
“A single-molecule photophysical study of a D-A-type conjugated polymer CzBT composed of an alkyne-linked 1,8-carbazole (Cz) and benzothiadiazole (BT) revealed unique intersegment interactions and a whole-chain conformation based on detailed spectroscopic characterization, including absorption and fluorescence spectra, fluorescence lifetime, and exciton migration that depend on the twist angle”
From The Pursuit of Shortwave Infrared-Emitting Nanoparticles with Bright Fluorescence through Molecular Design and Excited-State Engineering of Molecular Aggregates (2022) · cites this paper as [164]
A single-molecule photophysical study of the D-A-type conjugated polymer CzBT revealed unique intersegment interactions and a whole-chain conformation that depend on the twist angle between donor and acceptor.
“A single-molecule photophysical study of a D-A-type conjugated polymer CzBT composed of an alkyne-linked 1,8-carbazole (Cz) and benzothiadiazole (BT) revealed unique intersegment interactions and a whole-chain conformation based on detailed spectroscopic characterization, including absorption and fluorescence spectra, fluorescence lifetime, and exciton migration that depend on the twist angle”
From The Pursuit of Shortwave Infrared-Emitting Nanoparticles with Bright Fluorescence through Molecular Design and Excited-State Engineering of Molecular Aggregates (2022) · cites this paper as [150]
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Self-citation
- Authors
- Habuchi, S., Fujita, H., Michinobu, T., & Vacha, M.
- Affiliations
- Tokyo Institute of Technology (JP)
- Department of Organic and Polymeric Materials, Tokyo Institute of Technology, Ookayama, Meguro-ku, Tokyo 152-8552, Japan
- Corresponding author
- Habuchi, Satoshi
- Venue
- The Journal of Physical Chemistry B
- Publisher
- American Chemical Society (ACS)
- Published
- 2011-11-16
- Volume
- 115
- Issue
- 49
- Pages
- 14404-14415
- ISSN
- 1520-5207 (ISSN-L)
- 1520-6106
- OpenAlex
- W2329617519
- Cited by
- 39
- References
- 88
- Citations by year
- 2026: 2 · 2025: 1 · 2024: 1 · 2023: 2 · 2022: 3 · 2021: 2 · 2020: 2 · 2019: 5 · 2018: 3 · 2017: 2 · 2016: 3 · 2015: 2 · 2014: 2 · 2013: 4 · 2012: 5
- FWCI
- 2.46
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- The Journal of Physical Chemistry B (publishedVersion)
- PubMed (publishedVersion)
- Tokyo Tech Research Repository (Tokyo Institute of Technology) (submittedVersion)
- Funders
- Japan Society for the Promotion of Science (20340109, 22750122)
- Topics
- Physical Sciences › Engineering › Electrical and Electronic Engineering › Organic Electronics and Photovoltaics
- Physical Sciences › Chemistry › Physical and Theoretical Chemistry › Photochemistry and Electron Transfer Studies
- Physical Sciences › Engineering › Electrical and Electronic Engineering › Organic Light-Emitting Diodes Research
- Keywords
- donor-acceptor polymers, twist angle, benzothiadiazole, dimer structure, fluorescence lifetime distribution, fluorescence intensity ratio, exciton migration, exciton trapping, single-molecule fluorescence
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