Design of singlet fission chromophores with cyclic (alkyl)(amino) carbene building blocks

We use MRSF-TDDFT and NEVPT2 methods to design singlet fission chromophores with the building blocks of cyclic (alkyl)(amino)carbenes (CAACs). CAAC dimers with C₂, C₄, and p-phenylene spacers are considered. The substitutions with trifluoromethyls and fluorine atoms at the α C position are investigated. The electronegative substituents enhance the π accepting capability of the α C while maintaining it as a quaternary C atom. The phenylene-connected dimers with the two substitutions are identified as promising candidates for singlet fission chromophores. The cylindrically symmetric C₂ and C₄ spacers allow for substantial structural reorganizations in the S₀-to-S₁ and S₀-to-T₁ excitations. Although the two substituted dimers with the C₄ spacer satisfy (or very close to satisfy) the primary thermodynamics criterion for singlet fission, the significant structural reorganizations result in high barriers so that the fission is kinetically unfavorable.