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Ultrafast Time-resolved Near-IR Stimulated Raman Measurements of Functional π-conjugate Systems

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Real-Time Monitoring of Excited-State Ring-Puckering Process in BODIPY Molecule Using Ultrafast Spectroscopy.

Ayentika Sen^1,2, Aruna K Mora^2,3, Sukhendu Nath^2,3

¹Advanced Tunable Laser Applications Division, Bhabha Atomic Research Centre, Mumbai, India.

Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry

|June 5, 2026

Summary

Pyrromethene 597 (PM597) laser dye shows low fluorescence due to ultrafast excited-state decay. A ring-puckering process, sensitive to viscosity, causes this reduced emission efficiency.

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Area of Science:

Photochemistry
Spectroscopy
Materials Science

Background:

Pyrromethene 597 (PM597) is a common laser dye.
PM597 has lower fluorescence quantum yield than analogs like PM546 and PM560.

Purpose of the Study:

Investigate the mechanism behind PM597's reduced emission efficiency.
Elucidate the excited-state dynamics of PM597.

Main Methods:

Femtosecond fluorescence upconversion spectroscopy.
Transient absorption spectroscopy.
Viscosity-dependent studies in various solvents.

Main Results:

Identified ultrafast excited-state decay pathways in PM597.
Observed real-time formation of a new excited-state species via ring-puckering.
Determined the ring-puckering process has a time constant of ~1.3 ps in low-viscosity solvents.
Demonstrated substituent effects on the BODIPY ring influence ring-puckering.

Conclusions:

The low fluorescence of PM597 is attributed to an ultrafast excited-state ring-puckering process.
This process is highly sensitive to solvent viscosity.
Experimental findings align with theoretical predictions.