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Intermolecular Packing Effects on Singlet Fission in Oligorylene Dimers.

ABSTRACT: Using the density functional theory method, the crystalline packing effect on the singlet fission (SF) rate of oligorylenes, some of which are found to exhibit SF in crystal forms, is revealed by evaluating the effective electronic coupling (|V_eff|), the square of which is proportional to the SF rate. The |V_eff| values for terrylene and quaterrylene dimer models are investigated for a variety of slip-stacked forms. It is found that these values show similar dependences on the intermolecular packing as a function of lateral and longitudinal displacements of monomer frameworks, and that they are maximized in several configurations of one monomer slipped from another along the longitudinal axis. The present estimation method of the SF rate is also found to qualitatively explain the experimental SF rate difference between terrylene derivatives with different packing forms. Furthermore, by analyzing the effect of electronic couplings on the adiabatic electronic states related to SF, we predict several favorable molecular packings leading to a fast SF with a high triplet yield.

SUBMITTER: Nagami T

PROVIDER: S-EPMC6044983 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:Singlet fission is a process that splits collective excitations, or excitons, into two with unity efficiency. This exciton splitting process, unique to molecular photophysics, has the potential to considerably improve the efficiency of optoelectronic devices through more efficient light harvesting. While the first step of singlet fission has been characterized in great detail, subsequent steps critical to achieving overall highly-efficient singlet-to-triplet conversion are only just beginning to become well understood. One of the most elementary suggestions, which has yet to be tested, is that an appropriately balanced coupling is necessary to ensure overall highly efficient singlet fission; that is, the coupling needs to be strong enough so that the first step is fast and efficient, yet weak enough to ensure the independent behavior of the resultant triplets. In this work, we show how high overall singlet-to-triplet conversion efficiencies can be achieved in singlet fission by ensuring that the triplets comprising the triplet pair behave as independently as possible. We show that side chain sterics govern local packing in amorphous pentacene derivative nanoparticles, and that this in turn controls both the rate at which triplet pairs form and the rate at which they decay. We show how compact side chains and stronger couplings promote a triplet pair that effectively couples to the ground state, whereas bulkier side chains promote a triplet pair that appears more like two independent and long-lived triplet excitations. Our results show that the triplet pair is not emissive, that its decay is best viewed as internal conversion rather than triplet-triplet annihilation, and perhaps most critically that, in contrast to a number of recent suggestions, the triplets comprising the initially formed triplet pair cannot be considered independently. This work represents a significant step toward better understanding intermediates in singlet fission, and how molecular packing and couplings govern overall triplet yields.

Dataset Information

Intermolecular Packing Effects on Singlet Fission in Oligorylene Dimers.

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