Rapid Energy Transfer Enabling Control of Emission Polarization in Perylene Bisimide Donor–Acceptor Triads

Menelaou, Christopher; Schiphorst, Jeroen ter; Kendhale, Amol M.; Parkinson, Patrick; Debije, Michael G.; Schenning, Albertus P. H. J.; Herz, Laura M.

doi:10.1021/acs.jpclett.5b00183

Cited by 22 publications

(17 citation statements)

References 47 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…A negative anisotropy value suggests that a significant fraction of the emitting dipole moments are perpendicularly polarized to the absorbing transitions. 41 , 45 , 46 We can rule out unintentional excitation of the Q y state of the porphyrin monomers (polarized perpendicular to the ring plane) as a cause because the excitation energies employed here are substantially lower than the transition energy of the Q y state visible in absorption (2.1 eV).…”

mentioning

confidence: 92%

Breaking the Symmetry in Molecular Nanorings

Gong

Favereau

Anderson

et al. 2016

J. Phys. Chem. Lett.

Self Cite

View full text Add to dashboard Cite

Because of their unique electronic properties, cyclic molecular structures ranging from benzene to natural light-harvesting complexes have received much attention. Rigid π-conjugated templated porphyrin nanorings serve as excellent model systems here because they possess well-defined structures that can readily be controlled and because they support highly delocalized excitations. In this study, we have deliberately modified a series of six-porphyrin nanorings to examine the impact of lowering the rotational symmetry on their photophysical properties. We reveal that as symmetry distortions increase in severity along the series of structures, spectral changes and an enhancement of radiative emission strength occur, which derive from a transfer of oscillator strength into the lowest (k = 0) state. We find that concomitantly, the degeneracy of the dipole-allowed first excited (k = ±1) state is lifted, leading to an ultrafast polarization switching effect in the emission from strongly symmetry-broken nanorings.

show abstract

mentioning

confidence: 92%

Breaking the Symmetry in Molecular Nanorings

Gong

Favereau

Anderson

et al. 2016

J. Phys. Chem. Lett.

Self Cite

View full text Add to dashboard Cite

show abstract

“…A tendency toward a lower r value was observed at longer emission wavelengths [Figure d (ii)]. The gradual loss of fluorescence anisotropy at longer wavelengths is due to a coherent energy migration/transfer occurring in superhelical structures

true r = \frac{I_{V V} - G I_{V H}}{I_{V V} + 2 G I_{V H}}

true \frac{θ}{τ} = \frac{r}{r_{0} - r}

…”

Section: Resultsmentioning

confidence: 99%

Trismaleimide Dendrimers: Helix‐to‐Superhelix Supramolecular Transition Accompanied by White‐Light Emission

Wang

et al. 2019

Angewandte Chemie

View full text Add to dashboard Cite

Reported here are unprecedented fluorescent superhelices composed of primary, supramolecular polymers of the opposite helical twist. A new class of functional dendrimers was synthesized by amino‐ene click reactions, and they demonstrate an alternating OFF/ON fluorescence with generation growth. A peripherally alkyl‐modified dendrimer displays helix‐sense‐selective supramolecular polymerization, which predominantly forms right‐handed (or left‐handed) helical supramolecular polymers in the solution containing chiral solvents. With increasing the concentration, these primary helical supramolecular polymers spontaneously twist around themselves in the opposite direction to form superhelical structures. Atomic force microscopy and circular dichroism measurements were used to directly observe the helix‐to‐superhelix transition occurring with a reversal in the helical direction. Exceptional white‐light emission was observed during superhelix formation.

show abstract

“…[27] If the absorption by t-P12·(T6) 2 at 742 nm were entirely z-polarized, with emission entirely from astate polarized in the xy plane,then the anisotropy would be À0.2. [28] Thev alue of À0.04 reflects the presence of overlapping bands at 742 nm, with different polarizations.M igration of electronic excitation from the z-polarized staves to the xy-polarized state takes place faster than the 200 fs time resolution of our experiment.…”

Section: Angewandte Chemiementioning

confidence: 99%

A Molecular Nanotube with Three‐Dimensional π‐Conjugation

et al. 2015

Self Cite

View full text Add to dashboard Cite

A π‐conjugated twelve‐porphyrin tube is synthesized in 32 % yield by a template‐directed coupling reaction that joins together six porphyrin dimers, forming twelve new C—C bonds. The nanotube has two bound templates, enclosing an internal volume of approximately 4.5 nm3. Its UV/Vis/NIR absorption and fluorescence spectra resemble those of a previously reported six‐porphyrin ring, but are red‐shifted by approximately 300 cm−1, reflecting increased conjugation. Ultrafast fluorescence spectroscopy demonstrates extensive excited‐state delocalization. Transfer of electronic excitation from an initially formed state polarized in the direction of the nanotube axis (z axis) to an excited state polarized in the xy plane occurs within 200 fs, resulting in a negative fluorescence anisotropy on excitation at 742 nm.

show abstract

Rapid Energy Transfer Enabling Control of Emission Polarization in Perylene Bisimide Donor–Acceptor Triads

Cited by 22 publications

References 47 publications

Breaking the Symmetry in Molecular Nanorings

Breaking the Symmetry in Molecular Nanorings

Trismaleimide Dendrimers: Helix‐to‐Superhelix Supramolecular Transition Accompanied by White‐Light Emission

A Molecular Nanotube with Three‐Dimensional π‐Conjugation

Contact Info

Product

Resources

About