On couplings and excimers: Lessons from studies of singlet fission in covalently linked tetracene dimers

X. Feng and A.I. Krylov
Phys. Chem. Chem. Phys. 18, 7751 – 7761 (2016)

Electronic factors controlling singlet fission (SF) rates are investigated in covalently linked dimers of tetracene. Using covalent linkers, relative orientation of the individual chromophores can be controlled maximizing the rates of SF. Structures with coplanar and staggered arrangements of tetracene moieties are considered. The electronic structure calculations and three-state kinetic model for SF rates provide explanations for experimentally observed low SF yields in coplanar dimers and efficient SF in staggered dimers. The calculations illuminate the role of the excimer formation on SF. The structural relaxation in the S$_1$ state leads to the increased rate of the multi-exciton (ME) state formation, but impedes the second step, separation of the ME state into independent triplets. The slower second step reduces SF yield by allowing other processes, such as radiationless relaxation, to compete with triplet generation. The calculations of electronic couplings also suggest an increased rate of radiationless relaxation at the excimer geometries. Thus, the excimer serves as a trap of the ME state. The effect of covalent linkers on the electronic factors and SF rates is investigated. In all considered structures, the presence of the linker leads to larger couplings, however, the effect on the overall rate is less straightforward, since the linkers generally result in less favorable energetics. This complex behavior once again illustrates the importance of integrative approaches that evaluate the overall rate, rather than focusing on specific electronic factors such as energies or couplings.

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