Excitation Localization/Delocalization Isomerism in a Strongly Coupled Covalent Dimer of 1,3-Diphenylisobenzofuran

Schrauben, Joel N.; Akdağ, Akın; Wen, Jin; Havlas, Zdeněk; Ryerson, Joseph L.; Smith, Millie B.; Michl, Josef; Johnson, Justin C.

doi:10.1021/acs.jpca.6b00826

Cited by 38 publications

(37 citation statements)

References 43 publications

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“…For much of the history of SF, crystalline tetracene was the prototypical molecule where a m (T 1 T 1 ) state was invoked, with this state also having been explored in materials such as diphenylisobenzofuran. 24,25 However, the discovery of SF in non-crystalline systems has led to a huge increase in the number of systems with a resolvable and long-lived m (T 1 T 1 ) state. 13,[26][27][28][29][30][31][32] In the case of dimers (two covalently bound chromophores), the triplets generated are constrained to be adjacent to one another, and their proximity and orientation can be fine-tuned through chemical modifications.…”

Section: (T 1 T 1 ) In Molecular Materialsmentioning

confidence: 99%

Understanding the Bound Triplet-Pair State in Singlet Fission

Sanders

Pun

Parenti

et al. 2019

Chem

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Section: (T 1 T 1 ) In Molecular Materialsmentioning

confidence: 99%

Understanding the Bound Triplet-Pair State in Singlet Fission

Sanders

Pun

Parenti

et al. 2019

Chem

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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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“…Understanding how to control such dynamics is motivated by the premise that SF may serve as a means to down-convert higher energy solar photons into multiple electronic excitations rather than into a single excitation plus waste heat. 3 Dimer and small oligomer systems using acenes, [4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] but also diimides, 20 and isobenzofurans 21,22 are enabling the interrogation of numerous fundamental issues affecting SF rates and yields, including reaction thermodynamics, 6,[16][17][18]23 state couplings, 8,9,21,24,25 charge transfer intermediates, 10,[19][20][21] the role of entropy, 8 spin dynamics, 15,26 and exciton binding. 8,22,27 Within the overall body of dimer work in the literature, a leading role has been played by pentacene-based systems [5][6][7][10][11]…”

Section: Introductionmentioning

confidence: 99%

Using Structurally Well-Defined Norbornyl-Bridged Acene Dimers to Map a Mechanistic Landscape for Correlated Triplet Formation in Singlet Fission

et al. 2019

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Structurally well-defined TIPS-acetylene substituted tetracene (TIPS-BT1') and pentacene (TIPS-BP1') dimers utilizing a [2.2.1] bicyclic norbornyl bridge have been studiedprimarily using time-resolved spectroscopic methods -to uncover mechanistic details about primary steps in singlet fission leading to formation of the biexcitonic 1 TT state as well as decay pathways to the ground state. For TIPS-BP1' in room temperature toluene, 1 TT formation is rapid and complete, occurring in 4.4 ps. Decay to the ground state in 100 ns is the primary loss pathway for 1 TT in this system. For TIPS-BT1', the 1 TT is also observed to form rapidly (with a time constant of 5 ps) but in this case it occurs in concert with establishment of an excited state equilibrium (K~1) with the singlet exciton state S 1 at an energy of 2.3 eV above the ground state.The equilibrated states survive for 36 ns and are lost to ground state through both radiative and non-radiative pathways via the S 1 and non-radiative pathways via the 1 TT. The rapidity of 1 TT formation in TIPS-BT1' is at first glance surprising. However, our analysis suggests that the fewparameter rate constant expression of Marcus theory explains both individual and comparative findings in the set of systems, thus establishing benchmarks for diabatic coupling and reorganization energy needed for efficient 1 TT formation. Finally, a comparison of TIPS-BT1' with previous results obtained for a close constitutional isomer (TIPS-BT1) differing in the placement of TIPS-acetylene side groups suggests that the magnitude of exchange interaction in the correlated triplet manifold plays a critical role dictating 1 TT yield in the tetracenic systems.

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Excitation Localization/Delocalization Isomerism in a Strongly Coupled Covalent Dimer of 1,3-Diphenylisobenzofuran

Cited by 38 publications

References 43 publications

Understanding the Bound Triplet-Pair State in Singlet Fission

Understanding the Bound Triplet-Pair State in Singlet Fission

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

Using Structurally Well-Defined Norbornyl-Bridged Acene Dimers to Map a Mechanistic Landscape for Correlated Triplet Formation in Singlet Fission

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