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Distinct properties of the triplet pair state from singlet fission

M. Tuan Trinh; Andrew Pinkard; Andrew Brian Pun; Samuel Nathan Sanders; Elango Kumarasamy; Matthew Y. Sfeir; Luis M. Campos; Xavier Roy; Xiaoyang Zhu

Title:
Distinct properties of the triplet pair state from singlet fission
Author(s):
Trinh, M. Tuan
Pinkard, Andrew
Pun, Andrew Brian
Sanders, Samuel Nathan
Kumarasamy, Elango
Sfeir, Matthew Y.
Campos, Luis M.
Roy, Xavier
Zhu, Xiaoyang
Date:
Type:
Articles
Department(s):
Chemistry
Volume:
3
Persistent URL:
Book/Journal Title:
Science Advances
Abstract:
Singlet fission, the conversion of a singlet exciton (S1) to two triplets (2 × T1), may increase the solar energy conversion efficiency beyond the Shockley-Queisser limit. This process is believed to involve the correlated triplet pair state 1(TT). Despite extensive research, the nature of the 1(TT) state and its spectroscopic signature remain actively debated. We use an end-connected pentacene dimer (BP0) as a model system and show evidence for a tightly bound 1(TT) state. It is characterized in the near-infrared (IR) region (~1.0 eV) by a distinct excited-state absorption (ESA) spectral feature, which closely resembles that of the S1 state; both show vibronic progressions of the aromatic ring breathing mode. We assign these near-IR spectra to 1(TT)→Sn and S1→Sn′ transitions; Sn and Sn′ likely come from the antisymmetric and symmetric linear combinations, respectively, of the S2 state localized on each pentacene unit in the dimer molecule. The 1(TT)→Sn transition is an indicator of the intertriplet electronic coupling strength, because inserting a phenylene spacer or twisting the dihedral angle between the two pentacene chromophores decreases the intertriplet electronic coupling and diminishes this ESA peak. In addition to spectroscopic signature, the tightly bound 1(TT) state also shows chemical reactivity that is distinctively different from that of an individual T1 state. Using an electron-accepting iron oxide molecular cluster [Fe8O4] linked to the pentacene or pentacene dimer (BP0), we show that electron transfer to the cluster occurs efficiently from an individual T1 in pentacene but not from the tightly bound 1(TT) state. Thus, reducing intertriplet electronic coupling in 1(TT) via molecular design might be necessary for the efficient harvesting of triplets from intramolecular singlet fission.
Subject(s):
Chemistry
Triplet state
Energy conversion
Energy transfer
Solar thermal energy
Spectrum analysis
Publisher DOI:
https://doi.org/10.1126/sciadv.1700241
Item views
22
Metadata:
text | xml
Suggested Citation:
M. Tuan Trinh, Andrew Pinkard, Andrew Brian Pun, Samuel Nathan Sanders, Elango Kumarasamy, Matthew Y. Sfeir, Luis M. Campos, Xavier Roy, Xiaoyang Zhu, , Distinct properties of the triplet pair state from singlet fission, Columbia University Academic Commons, .

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