Singlet Fission in a covalently linked cofacial alkynyltetracene dimer

N.V. Korovina, S. Das, Z. Nett, X. Feng, J. Joy, A.I. Krylov, S.E. Bradforth, and M.E. Thompson
J. Am. Chem. Soc. 138, 617 – 627 (2016)

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 less than 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.

Download this paper (PDF)

Related Research

Computational studies of electronically excited and open-shell species: Jahn-Teller systems, radicals, diradicals and triradicals