Singlet Fission in a Covalently Linked Cofacial Alkynyltetracene Dimer
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- 作者：Nadezhda V. Korovina ; Saptaparna Das ; Zachary Nett ; Xintian Feng ; Jimmy Joy ; Ralf Haiges ; Anna I. Krylov ; Stephen E. Bradforth ; Mark E. Thompson
- 刊名：Journal of the American Chemical Society
- 出版年：2016
- 出版时间：January 20, 2016
- 年：2016
- 卷：138
- 期：2
- 页码：617-627
- 全文大小：659K
- ISSN：1520-5126
文摘
Singlet fission is a process in which a singlet exciton converts into two triplet excitons. To investigate this phenomenon, we synthesized two covalently linked 5-ethynyl-tetracene (ET) dimers with differing degrees of intertetracene overlap: BET-X, with large, cofacial overlap of tetracene π-orbitals, and BET-B, with twisted arrangement between tetracenes exhibits less overlap between the tetracene π-orbitals. The two compounds were crystallographically characterized and studied by absorption and emission spectroscopy in solution, in PMMA and neat thin films. The results show that singlet fission occurs within 1 ps in an amorphous thin film of BET-B with high efficiency (triplet yield: 154%). In solution and the PMMA matrix the S1 of BET-B relaxes to a correlated triplet pair 1(T1T1) on a time scale of 2 ps, which decays to the ground state without forming separated triplets, suggesting that triplet energy transfer from 1(T1T1) to a nearby chromophore is essential for producing free triplets. In support of this hypothesis, selective excitation of BET-B doped into a thin film of diphenyltetracene (DPT) leads to formation of the 1(T1T1) state of BET-B, followed by generation of both DPT and BET-B triplets. For the structurally cofacial BET-X, an intermediate forms in <180 fs and returns to the ground state more rapidly than BET-B. First-principles calculations predict a 2 orders of magnitude faster rate of singlet fission to the 1(T1T1) state in BET-B relative to that of crystalline tetracene, attributing the rate increase to greater coupling between the S1 and 1(T1T1) states and favorable energetics for formation of the separated triplets.