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The Molecular Origin
of Perylene Fluorescence in Gas,
Solution and Crystal Phases: A Comparative Theoretical Study
Irene Pusceddu (5420876)
Benedetta Bertoncini (18873314)
Davide Massafra (24657700)
Ilaria Ciofini (1294008)
Andrea Pucci (5444)
Carlo Adamo (1268928)
Michele Turelli (11141031)
Biophysics
Biochemistry
Physical Sciences not elsewhere classified
Medicine
Biotechnology
Chemical Sciences not elsewhere classified
materials science thanks
many optoelectronic applications
fundamental optical units
explicit vibrational effects
dependent optical response
coherent mechanism able
simulated spectra obtained
widespread molecular motif
corresponding molecular structures
different stacking configurations
aggregation phase determines
spectra observed
experimental spectra
emission spectra
molecular vibrations
molecular origin
work addresses
two minima
two elements
systematic assignment
strong coupling
pronounced interplay
level understanding
known “
give dimers
excited state
electronic structure
dual emission
dilute solutions
central role
Perylene is a widespread molecular motif in materials
science thanks
to its phase-dependent optical response and its good excitation transport
properties, making it ideal for many optoelectronic applications.
However, the molecular-level understanding of how changing the aggregation
phase determines the optical modulation remains elusive. This work
addresses this gap using density functional calculations at ground
and excited state. Using these data we present the systematic assignment
of experimental spectra in dilute solutions, dimeric aggregates and
the α-polymorph to the corresponding molecular structures through
a comparison to simulated spectra obtained with the inclusion of two
elements with pronounced interplay: (i) explicit vibrational effects,
arising from strong coupling between electronic structure and molecular
vibrations, and (ii) stacking of monomers in aggregates, to give dimers
as fundamental optical units. Incorporating these elements yields
accurate absorption and emission spectra and reveals the central role
of the dimer and of its different stacking configurations in the modulation
of the spectra observed in the crystal. The detailed structural data
generated allow us to hypothesize a coherent mechanism able to explain
the dual emission of α-perylene as based on the competition
of two minima on S<sub>1</sub>, ultimately identified as responsible
for the well-known “Y” and “E”-fluorescence.
2026-09-29T00:00:00Z
Text
Journal contribution
10.1021/acsaom.6c00444.s001
https://figshare.com/articles/journal_contribution/The_Molecular_Origin_of_Perylene_Fluorescence_in_Gas_Solution_and_Crystal_Phases_A_Comparative_Theoretical_Study/34028427
CC BY-NC 4.0