Tunable electronic coupling and driving force in structurally well-defined tetracene dimers for molecular singlet fission: a computational exploration using density functional theory.

Singlet fission (SF), a process by which two excited states are formed in a chromophoric system following the absorption of a single photon, has the potential to increase the theoretical efficiency of solar energy conversion devices beyond the single-junction Shockley-Quiesser limit. Although SF is observed with high yield in the solid state of certain molecules, linearly linked dimers based on these same constituents exhibit small yields in part due to small interchromophore electronic coupling. Previous work from our group demonstrated enhancement of SF yield in polycrystalline tetracene (Tc) via excitation of intermolecular motions, which increased direct overlap of monomer π-systems. In this current work, a series of norbornyl-bridged bistetracene (BT) dimers are investigated using DFT and the ability to control SF thermodynamics along with important interchromophore electronic coupling parameters via bridging geometry is shown. Although the electronic coupling of a series of C2v-symmetric dimers (BT1-BT3) that differ in norbornyl bridge length is larger than in previously studied Tc dimers, a key nonhorizontal electron-transfer (ET) matrix element used in determining the SF rate is zero due to symmetry. In these systems, SF may be expected but electronic excitation will require coupling to vibrational modes that break symmetry. Singly bridged dimer isomers BT1-trans and BT1-cis, which break the C2v symmetry of BT1 by exploiting attachment of the norbornyl bridge at the 1,2 instead of the 2,3 Tc positions, are expected to be significantly more favorable for SF due to an exoergic driving force, increased electronic coupling, a lower charge-transfer-state energy (particularly in the case of BT1-cis), and nonhorizontal ET matrix elements that are nonzero.