Fluorescence Studies of Terrylene in a Supersonic Jet:  Indication of A Dark Electronic State Below the Allowed Transition

Deperasińska, Irena; Zehnacker‐Rentien, Anne; Lahmani, F.; Borowicz, P.; Sepioł, Jerzy

doi:10.1021/jp070337o

Cited by 10 publications

(14 citation statements)

References 24 publications

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“…We studied several single Tr molecules and for all of them we observed these weak lines (with the experimental frequency reading precision of ±2 cm −1 ). Recently, the set of low-frequency modes (with the maxima at 56.6, 106.2, 160.6, and 199.4 cm −1 ) observed in the bulk fluorescence excitation spectrum of Tr in a supersonic jet expansion was attributed to nontotally symmetric vibronic transitions [15]. We postulate the same origin of the mentioned weak lines observed in our experiment.…”

Section: S-91supporting

confidence: 88%

“…In the spectra detected at high excitation intensity we observed some weak fluorescence excitation lines separated by 38, 67, 97, and 145 cm −1 from the (0,0) origin line. These lines were present in the spectra (measured in appropriate conditions) of the majority of studied single molecules and thus, we propose that they are nontotally symmetric low frequency vibration modes of Tr, recently observed in a supersonic jet expansion [15].…”

Section: Discussionsupporting

confidence: 57%

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Purely Electronic and Vibronic Fluorescence Excitation of Single Terrylene Molecules in a Naphthalene Crystal

et al. 2007

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Remembering Jurek Prochorow and many years in his groupFluorescence excitation spectra of spatially resolved single terrylene molecules in a naphthalene crystal were studied at 5 K as a function of exciting laser light intensity. The fully saturated fluorescence detection rate for purely electronic transition (0,0) was found to be about twice smaller than that for the two main vibronic components located 239 and 251 cm −1 above. This relation is fulfilled when the triplet population rate k23 is much weaker than the depopulation rate k 31 . We propose that the weak fluorescence excitation lines observed at the frequencies of 38, 67, 97, and 145 cm −1 correspond to nontotally symmetric low-frequency vibration modes of terrylene.

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Section: S-91supporting

confidence: 88%

Section: Discussionsupporting

confidence: 57%

Purely Electronic and Vibronic Fluorescence Excitation of Single Terrylene Molecules in a Naphthalene Crystal

et al. 2007

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“…[38] However, the distribution of linewidths is broader than that usually found in single crystals, as shown by the example of DBT in anthracene. For this measurement, the molecule was excited at 569.1 nm, which corresponds to one of the stronger vibrational modes determined from density functional theory (DFT) calculations [39] at 249 cm À1 above the ZPL 00 found at 577.1 nm. Extremely low interactions with low-frequency modes can induce line broadening as a result of dephasing.…”

Section: Capillary Samplementioning

confidence: 99%

Stable Single‐Molecule Lines of Terrylene in Polycrystalline para‐Dichlorobenzene at 1.5 K

et al. 2014

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The spectroscopic properties of single terrylene (Tr) molecules are studied in a polycrystalline matrix of para-dichlorobenzene (p-DCB) at 1.5 K. Samples grown in a glass capillary show a very strong site at 597 nm, which is redshifted by more than 700 cm(-1) from the observed transition energy for Tr in p-DCB prepared as a film on a coverslip (572 nm). Each of these two sites is characterized by measuring their single-molecule spectroscopic parameters at 1.5 K. Lifetime-limited linewidths of 45±5 MHz are found for both sites. Fluorescence detection rates reach 8×10(4) count s(-1) at saturation. The spectral trails of the majority of single molecules show no spectral jumps, indicating an absence of interacting two-level systems; however, the small distribution of linewidths may indicate weak interactions with low-frequency modes. Frequency jumps are observed for 10 % of the molecules. The complete emission spectra from two different single molecules at the center of each of the two sites is presented. Debye-Waller factors of αDW=0.33±0.05 for the normal site (572 nm) and αDW=0.30±0.05 for the red site (597 nm) are reported. This new host-guest system provides a quick and easy way to obtain lifetime-limited single-molecule lines.

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“…However, in helium buffer gas, Deperasińska et al found the indication of a dark electronic state below the dipole-allowed electronic state for jet-cooled terrylene. 27 The experimental findings indicate, for oligorylenes, subjected to the environment, that the orderings of the excited states could be changed. Theoretically Karabunarliev et al studied the oligorylenes by using different semiempirical and concluded that for quaterrylene, the optically opaque state becomes the lowest excited state adiabatically, not vertically, while for shorter rylenes, the lowest excited states are dipole-allowed both adiabatically and vertically.…”

Section: Introductionmentioning

confidence: 98%

Theoretical predictions of red and near-infrared strongly emitting X-annulated rylenes

Peng

Niu

Wang

et al. 2011

The Journal of Chemical Physics

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The optical properties of rylenes are extremely interesting because their emission colors can be tuned from blue to near-infrared by simply elongating the chain length. However, for conjugated chains, the dipole-allowed odd-parity 1B u excited state often lies above the dipole-forbidden evenparity 2A g state as the chain length increases, thus preventing any significant luminescence according to Kasha's rule. We systemically investigated the 1B u /2A g crossover behaviors with respect to the elongating rylene chain length with various quantum chemistry approaches, such as timedepended density functional theory (TDDFT), complete active space self-consistent field theory (CASSCF/CASPT2), multireference configuration interaction (MRCI)/Zerner's intermediate neglect of diatomic overlap (ZINDO), and MRCI/modified neglect of differential overlap. The calculated results by CASSCF/CASPT2 and MRCI/ZINDO are completely coherent: the optical active 1B u state lies below the dark B 3g or 2A g state for perylene and terrylene, which results in strong fluorescence; while a crossover to S 1 = 2A g occurs and leads to much weaker fluorescence for quaterrylene. Then we put forward a molecular design rule on how to recover fluorescence for the longer rylenes by introducing heteroatom bridges. Several heteroatom-annulated rylenes are designed theoretically, which are predicted to be strongly emissive in the red and near-infrared ranges. These are further confirmed by theoretical emission spectra as well as radiative and nonradiative decay rate calculations by using the vibration correlation function formalisms we developed earlier coupled with TDDFT.

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Fluorescence Studies of Terrylene in a Supersonic Jet: Indication of A Dark Electronic State Below the Allowed Transition

Cited by 10 publications

References 24 publications

Purely Electronic and Vibronic Fluorescence Excitation of Single Terrylene Molecules in a Naphthalene Crystal

Purely Electronic and Vibronic Fluorescence Excitation of Single Terrylene Molecules in a Naphthalene Crystal

Stable Single‐Molecule Lines of Terrylene in Polycrystalline para‐Dichlorobenzene at 1.5 K

Theoretical predictions of red and near-infrared strongly emitting X-annulated rylenes

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