Decakis(arylthio)corannulenes: Transferable Photochemical and Redox Parameters and Photovoltaic Device Performance

Deng, Yongbo; Xu, Bokai; Castro, Edison; Fernandez‐Delgado, Olivia; Echegoyen, Luís; Baldridge, Kim K.; Siegel, Jay S.

doi:10.1002/ejoc.201700861

Cited by 17 publications

(16 citation statements)

References 24 publications

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“…The so‐called “optical band gap”, defined either from the long‐wave absorption maxima or from the onsets of these bands, can thus be calculated as 2.82–2.84 or 2.37–2.38 eV, respectively. This lack of sensitivity towards substituent effects is in sharp contrast to the above‐mentioned observation with metal‐free persulfurated arenes, but confirms the old observation for ferrocenes that this band is “relatively insensitive to substitution on the ring” . Also not very astonishing, both compounds showed neither fluorescence nor phosphorescence.…”

Section: Methodssupporting

confidence: 83%

“…Dendrimers with a [C 6 (SAr) 6 ] core, so‐called “molecular asterisks” have been used as multifunctional ligands for the preparation of luminescent sensors and asymmetric metal catalysis . The interesting electronic properties shared by this compound class are mainly due to the fact that “phenylthio substituents attached to aromatic cores result in a reduction of the HOMO–LUMO gap”, “primarily due to LUMO stabilization” . Upon addition of SPh groups a bathochromic shift of the longest wavelength absorption by 10–15 nm is observed together with an increase of the reduction potential by 0.1 V …”

Section: Methodsmentioning

confidence: 99%

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Ferrocenes with a Persulfurated Cyclopentadienyl Ring: Synthesis, Structural Studies, and Optoelectronic Properties

Blockhaus

Klein-Heßling

Zehetmaier

et al. 2019

Chemistry A European J

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Persulfurateda renes are af ascinating class of functional molecules with aw ider ange of potentiala pplications. Ferrocenes are also am ultifaceted class of aromatic compounds that can easily be finetuned for an enormous variety of desired properties. Ac ombinationo f both substancec lasses might yield an even wider field of applications. Herein, we describe the synthesis of two ferrocenesw ith one persulfurated cyclopentadienyl ring [C 5 (SR) 5 ], with R = Me or Ph, together with their crystal structures, optical, and electrochemical properties. Both crystal structures show significant intramolecular sulfuriron interactions as well as weak intermoleculars ulfurcontacts. Cyclovoltammetry of the [C 5 (SPh) 5 ]c ompound shows ah igho xidationp otentialo f6 51 mV vs. FcH/FcH + .Persulfurated arenes still remain an underexploited field of chemistry,d espite their highly interesting physical organic properties and their numerous possible applications, ranging from ion-selectivem embranes over organic conductors and ferromagnets to cation sensors andl iquid crystals. [1] This statement made by M. Gingras in af ascinatingr eview article in this journal more than 10 years ago is still valid. There have been, however,s everali nteresting additions to this field, particularly with extended aromatic systems. Per(arylthio)corannulenes and -coronenes have found potential applicationa sp hotovoltaic devices [2] and for molecular electronics. [3] Substituted hexakis(phenylthio)benzenes showeds trong phosphorescence in the solid state with the potential of OLED applications. [4] Dendrimersw ith a[ C 6 (SAr) 6 ]c ore, so-called" molecular asterisks" have been used as multifunctional ligandsf or the preparation of luminescents ensors and asymmetric metal catalysis. [5] The interesting electronic properties sharedb yt his compound class are mainly due to the fact that "phenylthio substituents attached to aromatic cores result in ar eduction of the HOMO-LUMOg ap", [1, 2a] "primarily due to LUMO stabilization". [6] Upon addition of SPh groups ab athochromic shift of the longest wavelength absorption by 10-15 nm is observed together with an increaseofthereductionpotential by 0.1 V. [2b] Metallocenes are another very important group of aromatics with very interestinge lectronic properties. However,w hile quite af ew metal-freep ersulfurated arenes have been studied, there seem to be no reports of persulfuratedferrocenes. The fivefolds ymmetry of metallocenes would create as tructural motifr arely found with thioether-based "moleculara sterisks" (Scheme 1). [7] While the syntheses of persulfurated cyclopentadienyl anions[ C 5 (SR) 5 ] À (R = Me, Ph) was already reported in the 1980s, [8] attempts to prepare metallocenes from them via reactions with metal halidesm et with failure. However,t he complexes[ C 5 (SMe) 5 ]ML n (ML n = Mn(CO) 3 ,R uCp*) could be obtainedv ia post-functionalization of an already coordinated cyclopentadienyl ring. [9,10] Transfer of this syntheticp rotocol using perhalogenatedo rp ermercurated ferroce...

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Section: Methodssupporting

confidence: 83%

Section: Methodsmentioning

confidence: 99%

Ferrocenes with a Persulfurated Cyclopentadienyl Ring: Synthesis, Structural Studies, and Optoelectronic Properties

Blockhaus

Klein-Heßling

Zehetmaier

et al. 2019

Chemistry A European J

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“…The absorption maximum is observed at 503 nm with an extinction coefficient of 44,600 M À1 cm À1 (Table S1). Due to the electron-poor naphthalimide annulation of the electron-rich corannulene core, which leads to an extension of the π-system, the absorption is significantly red-shifted compared to the parent corannulene and Suzuki-coupled derivatives, 24 as well as the monoannulated derivative. 25 Even more important is the huge increase in absorptivity with respect to the benchmark acceptor C 60 , which should augment the lightharvesting ability in an OSC (Figure 1).…”

Section: Resultsmentioning

confidence: 99%

Bowl-Shaped Naphthalimide-Annulated Corannulene as Nonfullerene Acceptor in Organic Solar Cells

et al. 2020

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An electron-poor bowl-shaped naphthalimide-annulated corannulene with branched alkyl residues in the imide position was synthesized by a palladium-catalyzed cross-coupling annulation sequence. This dipolar compound exhibits strong absorption in the visible range along with a low-lying LUMO level at –3.85 eV, enabling n-type charge transport in organic thin-film transistors. Furthermore, we processed inverted bulk-heterojunction solar cells in combination with the two donor polymers PCE–10 and PM6 to achieve open-circuit voltages up to 1.04 V. By using a blend of the self-assembled naphthalimide-annulated corannulene and PCE–10, we were able to obtain a power conversion efficiency of up to 2.1%, which is to the best of our knowledge the highest reported value for a corannulene-based organic solar cell to date.

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“…Siegel observed that decakis(arylsuldo)-corannulene (7, Fig. 2) exhibits quite a shallow bowl (0.486Å), 64,74 even though the steric demands of a phenyl ring are not very high. Encouraged by this observation, we assumed that ten t-butylsuldo groups on the corannulene rim would exert sufficiently high steric demands to atten the bowl.…”

Section: Theoretical Predictionsmentioning

confidence: 99%

Flat corannulene: when a transition state becomes a stable molecule

et al. 2020

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Decakis(arylthio)corannulenes: Transferable Photochemical and Redox Parameters and Photovoltaic Device Performance

Abstract: Absorption and redox properties of seven decakis(phenylthio)corannulene derivatives 3a–3g lead to a model for estimating material properties in persulfurated aromatic compounds. The same series is evaluated for performance in bulk heterojunction and perovskite photovoltaic devices.

Cited by 17 publications

References 24 publications

Ferrocenes with a Persulfurated Cyclopentadienyl Ring: Synthesis, Structural Studies, and Optoelectronic Properties

Ferrocenes with a Persulfurated Cyclopentadienyl Ring: Synthesis, Structural Studies, and Optoelectronic Properties

Bowl-Shaped Naphthalimide-Annulated Corannulene as Nonfullerene Acceptor in Organic Solar Cells

Flat corannulene: when a transition state becomes a stable molecule

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