Singlet Fission in Polypentacene

Sanders, Samuel N.; Kumarasamy, Elango; Pun, Andrew B.; Steigerwald, Michael L.; Sfeir, Matthew Y.; Campos, Luis M.

doi:10.1016/j.chempr.2016.08.016

Cited by 71 publications

(102 citation statements)

References 38 publications

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“…Delocalized over four chromophores, iSF in PT offers six different pairs of pentacenes in a favored orientation: [( T 1 T 1 S 0 S 0 ), ( T 1 S 0 T 1 S 0 ), ( T 1 S 0 S 0 T 1 ), (S 0 T 1 S 0 T 1 ), (S 0 T 1 T 1 S 0 ), (S 0 S 0 T 1 T 1 )], thus leading to a higher rate of iSF for PT than PD , as well as a concurrent increase in the rate constant of SF ( k SF ) by a factor of approximately 3, from 2.3×10 9 ( PD ) to 6.8×10 9 s −1 ( PT ). This finding is in line with results for oligomeric pentacenes . Solvent polarity also dictates k SF , with values in toluene of 1.2×10 9 and 3.3×10 9 s −1 for PD and PT , respectively, thus suggesting a superexchange mechanism .…”

Section: Figuresupporting

confidence: 90%

Chromophore Multiplication To Enable Exciton Delocalization and Triplet Diffusion Following Singlet Fission in Tetrameric Pentacene

Hetzer

Basel²,

Kopp

et al. 2019

Angewandte Chemie

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Atetrameric pentacene, PT,has been used to explore the effects of exciton delocalization on singlet fission (SF). For the first time,t riplet decorrelation through intramolecular triplet diffusion was observed following SF.T ransient absorption spectroscopyw as used to examine different decorrelation mechanisms (triplet diffusion versus structural changes) for PT and its dimeric equivalent PD on the basis of the rate and activation barrier of the decorrelation step.Charge-separation experiments using tetracyano-p-quinodimethane (TCNQ)t o quencht riplet excitons formed through SF demonstrate that enhanced intersystem crossing, that is,spin catalysis,isawidely underestimated obstacle to quantitative harvesting of the SF products.The importance of spatial separation of the decorrelated triplet states is emphasized, and independent proof that the decorrelated triplet pair state consists of two (T 1 )states per molecule is provided.

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Section: Figuresupporting

confidence: 90%

Chromophore Multiplication To Enable Exciton Delocalization and Triplet Diffusion Following Singlet Fission in Tetrameric Pentacene

Hetzer

Basel²,

Kopp

et al. 2019

Angewandte Chemie

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“…Many of these syntheses rely on metal-catalyzed cross-coupling protocols such as the Suzuki and Sonogashira reactions, althoughi nnovatives ynthe-ses based on, for example, Diels-Alder cycloadditions [53] have recently appeared. Beyond pentacene, av ariety of other carbon-rich oligomeric chromophores have been explored for iSF and contribute to unraveling the underlying mechanism, these reports are outside the scope of this Minireview,a nd for current examples, see references [54][55][56][57][58][59][60][61][62][63][64][65][66][67].…”

Section: Introductionmentioning

confidence: 99%

Pentacene Dimers as a Critical Tool for the Investigation of Intramolecular Singlet Fission

Hetzer

Guldi

Tykwinski

2018

Chemistry A European J

132

176

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Singlet fission (SF) involves the spontaneous splitting of a photoexcited singlet state into a pair of triplets, and it holds great promise toward the realization of more efficient solar cells. Although the process of SF has been known since the 1960s, debate regarding the underlying mechanism continues to this day, especially for molecular materials. A number of different chromophores have been synthesized and studied in order to better understand the process of SF. These previous reports have established that pentacene and its derivatives are especially well-suited for the study of SF, since the energetic requirement E(S )≥2E(T ) is fulfilled rendering the process exothermic and unidirectional. Dimeric pentacene derivatives, in which individual pentacene chromophores are tethered by a "spacer", have emerged as the system of choice toward exploring the mechanism of intramolecular singlet fission (iSF). The dimeric structure, and in particular the spacer, allows for controlling and tuning the distance, geometric relationship, and electronic coupling between the two pentacene moieties. This Minireview describes recent advances using pentacene dimers for the investigation of iSF.

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“…Oligoacenes [23][24][25][26][27][28][29][30][31][32][33][34] and their derivatives 35,36 stand out among organic chromophores and have been pivotal in fundamental research of SF. Both tetracene [37][38][39][40][41] and pentacene [42][43][44] are top performers, exhibiting fast SF and near 200% triplet yield.…”

Section: Introductionmentioning

confidence: 99%

On the possibility of singlet fission in crystalline quaterrylene

Wang

Liu

Cook

et al. 2018

The Journal of Chemical Physics

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Singlet fission (SF), the spontaneous down-conversion of a singlet exciton into two triplet excitons residing on neighboring molecules, is a promising route to improve organic photovoltaic (OPV) device efficiencies by harvesting two charge carriers from one photon. However, only a few materials have been discovered that exhibit intermolecular SF in the solid state, most of which are acene derivatives. Recently, there has been a growing interest in rylenes as potential SF materials. We use many-body perturbation theory in the GW approximation and the Bethe-Salpeter equation to investigate the possibility of intermolecular SF in crystalline perylene and quaterrylene. A new method is presented for determining the percent charge transfer (%CT) character of an exciton wave-function from double-Bader analysis. This enables relating exciton probability distributions to crystal packing. Based on comparison to known and predicted SF materials with respect to the energy conservation criterion (E-2E) and %CT, crystalline quaterrylene is a promising candidate for intermolecular SF. Furthermore, quaterrylene is attractive for OPV applications, thanks to its high stability and narrow optical gap. Perylene is not expected to exhibit SF; however, it is a promising candidate for harvesting sub-gap photons by triplet-triplet annihilation.

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Singlet Fission in Polypentacene

Cited by 71 publications

References 38 publications

Chromophore Multiplication To Enable Exciton Delocalization and Triplet Diffusion Following Singlet Fission in Tetrameric Pentacene

Chromophore Multiplication To Enable Exciton Delocalization and Triplet Diffusion Following Singlet Fission in Tetrameric Pentacene

Pentacene Dimers as a Critical Tool for the Investigation of Intramolecular Singlet Fission

On the possibility of singlet fission in crystalline quaterrylene

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