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Combining high electron affinity and intramolecular charge transfer in 1,3-dithiole-nitrofluorene push-pull diads
Dmitrii F Perepichka1, Igor F Perepichka, Oleksandr Ivasenko
1Department of Chemistry, McGill University, 801 Sherbrooke Street West, Montreal H3A 2K6, QC, Canada. dmitrii.perepichka@mcgill.ca
New conjugated compounds with high electron affinity and intramolecular charge transfer (ICT) show promise for optoelectronics. These fluorene-dithiole derivatives significantly enhance photosensitivity in storage media.
Area of Science:
- Organic Chemistry
- Materials Science
- Optoelectronics
Background:
- Intramolecular charge transfer (ICT) is crucial for designing advanced optoelectronic materials.
- Polynitrofluorene derivatives offer potential as electron acceptors due to their high electron affinity.
Purpose of the Study:
- To synthesize and characterize novel conjugated compounds by linking electron-rich 1,3-dithiol-2-ylidene moieties to polynitrofluorene acceptors.
- To investigate the relationship between molecular structure, ICT properties, and optoelectronic performance.
- To explore the potential applications of these compounds in photothermoplastic storage media.
Main Methods:
- Synthesis of highly conjugated fluorene-dithiole derivatives (compounds 6-11).
- Spectroscopic analysis (UV-Vis) to observe ICT-related absorption bands.
- Electrochemical measurements to determine reduction potentials.
- X-ray crystallographic analysis to confirm molecular structure and ICT interactions.
- Incorporation into photoconductive films to evaluate photosensitivity.
Main Results:
- Compounds 6-11 exhibit strong ICT, evidenced by intense visible absorption bands.
- Fluorene-dithiole derivative 6a significantly improved photosensitivity in photothermoplastic storage media.
- A strong correlation was found between ICT energy, reduction potential, and Hammett's parameters.
- X-ray crystallography confirmed ICT in the ground state and revealed an elongated C9=C14 bond, sensitive to dithiole moiety character.
- A blueshift in the ICT band upon heating suggests increased twisting around the C9=C14 bond.
Conclusions:
- The synthesized fluorene-dithiole compounds possess a unique combination of high electron affinity and ICT, making them suitable for optoelectronic applications.
- These materials demonstrate enhanced performance in photothermoplastic storage media due to their ICT properties.
- Structural modifications effectively tune the electronic and optical properties, offering a pathway for designing tailored optoelectronic materials.
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