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Unusual Nonemissive Behavior of Rubrene J-Aggregates: A Rare Violation
Nikhil Aggarwal,
Published in American Chemical Society
2017
PMID: 28334526
Volume: 121
   
Issue: 14
Pages: 3190 - 3201
Abstract
Structure-property correlations in rubrene (RB) colloidal J-aggregates were unravelled by steady state and time-resolved spectroscopy in conjunction with excited state density functional calculations. The RB J-aggregate with a slippage angle θ = 30.4°, estimated from the monomeric transition dipole moment directions, exhibited a broad fwhm of 1073 cm-1 and a 5 nm red-shifted absorption band carrying a transition dipole moment (M→ - λagg = 1.80 D) almost equivalent to the monomeric dye (M→ - λmon = 1.89 D). A significantly low magnitude of exciton coupling energy, ΔEexc = -358 cm-1 for the rhombic-RB colloidal J-aggregates resulted owing to the weaker electronic communication between the largely separated RB subunits (r = 7.2 Å) and a restricted exciton delocalization over the RB J-dimer (N = 2). The RB J-dimer exhibited a perfect balance between the computed singlet (2.53 eV) and the triplet (1.29 eV) exciton energies for singlet fission (SF). Supporting this, the PL decay profile of the J-aggregates revealed a delayed fluorescence, substantiating triplet pair formation via SF. The experimental evidence for the long-lived triplet formation was furthermore confirmed by its transient absorption (T1 → TN) at 530 nm. Consequently, a high probability for SF and a low probability for triplet-triplet recombination, leading to a dramatic lowering in photoluminescence quantum yield from 0.172 down to 0.035 was noted. The electronic structure calculations for the RB J-dimer followed TD-DFT-M062X/6-31G+(d,p) level of theory following integral equation formalism polarizable continuum model (IEFPCM) in water. S1 excited state for RB J-dimer was carefully analyzed using integral overlap of electron and hole density distribution (φ) and the defined t-indexes along all three spatial directions, and was found to be of locally excited in character. © 2017 American Chemical Society.
About the journal
JournalData powered by TypesetJournal of Physical Chemistry B
PublisherData powered by TypesetAmerican Chemical Society
ISSN15206106
Open AccessNo
Concepts (19)
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    Aggregates
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    Continuum mechanics
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    Dimers
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    Dipole moment
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    Dyes
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    Electronic structure
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    Excitons
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    Fluorescence
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    Integral equations
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    Laser spectroscopy
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    Electronic communications
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    Electronic structure calculations
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    INTEGRAL EQUATION FORMALISMS
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    PHOTOLUMINESCENCE QUANTUM YIELDS
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    Polarizable continuum model
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    Structure-property correlation
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    TIME-RESOLVED SPECTROSCOPY
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    TRANSITION DIPOLE MOMENTS
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    Excited states