High‐Resolution Electronic Excitation and Emission Spectra of Pentacene and 6,13‐Diazapentacene Monomers and Weakly Bound Dimers by Matrix‐Isolation Spectroscopy

Thusek, Jean; Hoffmann, Marvin; Hübner, Olaf; Germer, Stefan; Hoffmann, Hendrik; Freudenberg, Jan; Bunz, Uwe H. F.; Dreuw, Andreas; Himmel, Hans‐Jörg

doi:10.1002/chem.202003999

Cited by 12 publications

(24 citation statements)

References 73 publications

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“…Similar to the linear acenes, the absorption spectra of the azabisacenes display well‐resolved “acene fingers” (p‐bands) with the most dominant contribution involving the two vibrational ground states of S 0 →S 1 , attributable to a HOMO‐LUMO transition as evidenced by quantum‐chemical TD‐DFT calculations (see Section S7 in the Supporting Information). [ 23 , 24 ] This is in accordance with the findings of Briseno et al. for A .…”

supporting

confidence: 92%

TIPS‐Ethynylated Naphthodiquinoline and Naphthodiacridine: Novel Diazabisacenes

Ahrens

Maier

Misselwitz

et al. 2021

Chemistry A European J

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The synthesis of two diazabisacenes is reported. A bisboronated naphthalene was Suzuki-coupled to substituted ethyl nicotinates, then cyclized by intramolecular Friedel-Crafts acylation. The resulting diketones were alkynylated and reduced to give the title compounds, bis (TIPS-ethynyl)-substituted naphtha[1,8-gh:5,4-g'h']diquinoline and naphtho[1,8-bc:5,4-b'c']diacridine. Nitrogen incorporation stabilizes the bisacenes with respect to oxidation compared to their consanguine nonaza analogs.

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supporting

confidence: 92%

TIPS‐Ethynylated Naphthodiquinoline and Naphthodiacridine: Novel Diazabisacenes

Ahrens

Maier

Misselwitz

et al. 2021

Chemistry A European J

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“…In fact, our findings are well in line with previous studies 29−33 on high-resolution electronic spectrum of pentacene whose vibronic peaks can be faithfully resolved at the FC level 34 except for one that is at ∼100 cm −1 to the blue side of the 0 → 0 transition. 30 That missing peak in the single-molecule simulation result has been ascribed to the Htype dimerization of pentacene in the neon matrix. 30 Most recently, the HT effect for two selected vibrational modes of pentacene was imaged by position-dependent scanning tunneling microscope induced luminescence (STML), 35 revealing distinct patterns of vibration-induced transition charges.…”

Section: Vibrational Resolution Of Absorptionmentioning

confidence: 99%

“…30 That missing peak in the single-molecule simulation result has been ascribed to the Htype dimerization of pentacene in the neon matrix. 30 Most recently, the HT effect for two selected vibrational modes of pentacene was imaged by position-dependent scanning tunneling microscope induced luminescence (STML), 35 revealing distinct patterns of vibration-induced transition charges.…”

Section: Vibrational Resolution Of Absorptionmentioning

confidence: 99%

Symmetry-Breaking Enhanced Herzberg–Teller Effect with Brominated Polyacenes

et al. 2021

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Molecular symmetry is vital to the selection rule of vibrationally resolved electronic transition, particularly when the nuclear dependence of electronic wave function is explicitly treated by including Franck–Condon (FC) factor, Franck–Condon/Herzberg–Teller (FC/HT) interference, and Herzberg–Teller (HT) coupling. Our present study investigated the light absorption spectra of highly symmetric tetracene, pentacene, and hexacene molecules of point-group D 2h , as well as their monobrominated derivatives with a lower C s symmetry. It was found that the symmetry-breaking monobromination allows more vibrational normal modes and their pairs to contribute to FC/HT interference and HT coupling, respectively. Through a projection of a molecule’s vibrational normal modes to its irreducible representations, a linear relationship between the FC/HT intensity to the polyacene’s size was deduced alongside a quadratic dependence of the HT intensity. Both theoretically derived correlations were well justified by our numerical simulations, which also demonstrated an approximately 20% improvement on the agreement with experimental line shape if the HT theory is adopted to replace the FC approximation. Moreover, for these low-symmetry monobrominated polyacenes, the FC intensity was even weaker than its FC/HT and HT counterparts at some excitation energies, making the HT theory imperative to decipher vibronic coupling, a fundamental driving force behind numerous chemical, biological, and photophysical processes.

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“…Therefore, in order to access such data, in general, the matrix isolation technique is exploited to record the high resolution absorption spectra at very low temperatures and in gaseous matrices. [70][71][72] The limited availability of such experimental spectra may hamper the wide scope applicability of the presented method, but this is only true for relatively large molecules with many vibrational degrees of freedom. The excited state geometry of small molecules with fewer vibrational modes can always be predicted as long as there is some discernible vibronic progression present in the experimental absorption spectra.…”

Section: Advantages and Limitations Of Proposed Theoretical Approachmentioning

confidence: 99%

“…Some experimental spectra clearly show the presence of hot bands [73] or vibrational progressions belonging to dimeric species. [70,71] Therefore, the applied theoretical model should account for those features in the optical spectra in order to obtain satisfactory fitting results.…”

Section: Advantages and Limitations Of Proposed Theoretical Approachmentioning

confidence: 99%

How to Predict Excited State Geometry by Using Empirical Parameters Obtained from Franck‐Condon Analysis of Optical Spectrum

Köse

2021

ChemPhysChem

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Excited state geometries of molecules can be calculated with highly reliable wavefunction schemes. Most of such schemes, however, are applicable to small molecules and can hardly be viewed as error-free for excited state geometries. In this study, a theoretical approach is presented in which the excited state geometries of molecules can be predicted by using vibrationally resolved experimental absorption spectrum in combination with the theoretical modelling of vibrational pattern based on Franck-Condon approximation. Huang-Rhys factors have been empirically determined and used as input for revealing the structural changes occurring between the ground and the excited state geometries upon photoexcitation. Naphthalene molecule has been chosen as a test case to show the robustness of the proposed theoretical approach. Predicted 1B 2u excited state geometry of the naphthalene has similar but slightly different bond length alternation pattern when compared with the geometries calculated with CIS, B3LYP, and CC2 methods. Excited state geometries of perylene and pyrene molecules are also determined with the presented theoretical approach. This powerful method can be applied to other molecules and specifically to relatively large molecules rather easily as long as vibrationally resolved experimental spectra are available to use.

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High‐Resolution Electronic Excitation and Emission Spectra of Pentacene and 6,13‐Diazapentacene Monomers and Weakly Bound Dimers by Matrix‐Isolation Spectroscopy

Cited by 12 publications

References 73 publications

TIPS‐Ethynylated Naphthodiquinoline and Naphthodiacridine: Novel Diazabisacenes

TIPS‐Ethynylated Naphthodiquinoline and Naphthodiacridine: Novel Diazabisacenes

Symmetry-Breaking Enhanced Herzberg–Teller Effect with Brominated Polyacenes

How to Predict Excited State Geometry by Using Empirical Parameters Obtained from Franck‐Condon Analysis of Optical Spectrum

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