Carbene-Metal-Amide Bond Deformation, Rather Than Ligand Rotation, Drives Delayed Fluorescence.

ABSTRACT

We report three characteristics of ideal thermally activated delayed fluorescence molecular systems apparent in carbene-metal-amides (a) an exceptionally small singlet-triplet gap that effectively eliminates the thermal activation barrier to reverse intersystem crossing; (b) significant singlet oscillator strength promoting fluorescence in the region of this small barrier; and (c) enlarged spin-orbit coupling driving reverse intersystem crossing in this region. We carry out highly correlated quantum-chemical calculations to detail the relative energies of and spin-orbit couplings between the singlet and triplet states, finding that they fall closer together in energy and couple more strongly in going from the singlet ground-state to the triplet optimized geometry. This structural reorganization is defined not by rotation of the ligands but by a nontrivial bending of the carbene-metal-amide bond angle. This bending reduces carbene-metal-amide symmetry and enhances singlet-triplet interaction strength. We clarify that the reverse intersystem crossing triggering delayed fluorescence occurs around the coplanar triplet geometric optimum.