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From solution to thin films: unravelling excited-state behaviour in halogenated diradicaloids
Matteo Bevilacqua1, Luca Ciuffarin2, Roberto Costantini2,3
1Dipartimento di Scienze Chimiche, Università degli Studi di Padova, via F. Marzolo 1, Padova, 35131, Italy. marco.baron@unipd.it.
Chemical Communications (Cambridge, England)
|February 10, 2026
Summary
Stable fluorine and chlorine diradicaloids show charge-separated states in solution. In thin films, however, short-lived singlets dominate, limiting singlet fission potential for optoelectronics.
Area of Science:
- Organic chemistry
- Materials science
- Photophysics
Background:
- Thiele-like diradicaloids are promising organic molecules for optoelectronic applications.
- Understanding their excited-state dynamics in different phases is crucial for device implementation.
Purpose of the Study:
- To synthesize and investigate the photophysical properties of fluorine and chlorine decorated Thiele-like diradicaloids.
- To compare their excited-state behavior in solution versus thin films.
Main Methods:
- Synthesis of novel diradicaloid compounds.
- Femtosecond transient absorption spectroscopy.
- Solid-state thin film characterization.
Main Results:
- Diradicaloids exhibited charge-separated states in solution.
- In thin films, only short-lived singlets were observed, with no evidence of intermediates.
- Strong intermolecular interactions in the solid state suppressed excited-state dynamics.
Conclusions:
- The solid-state environment significantly alters the excited-state dynamics of these diradicaloids.
- Suppressed dynamics limit their potential for singlet fission in solid-state optoelectronic devices.
- Design strategies must address intermolecular interactions for effective solid-state applications.
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