Thiocarbonyl-Bridged N-Heterotriangulenes for Energy Efficient Triplet Photosensitization: A Theoretical Perspective.

Structurally-rigid metal-free organic molecules are of high demand for various triplet harvesting applications. However, inefficient intersystem crossing (ISC) due to large singlet-triplet gap ( Δ E S - T ${\Delta {E}_{S-T}}$ ) and small spin-orbit coupling (SOC) between lowest excited singlet and triplet often limits their efficiency. Excited electronic states, fluorescence and ISC rates in several thiocarbonyl-bridged N-heterotriangulene ( m ${m}$ S-HTG) with systematically increased thione content ( m = ${m=}$ 0-3) are investigated implementing polarization consistent time-dependent optimally-tuned range-separated hybrid. All m ${m}$ S-HTGs are dynamically stable and also thermodynamically feasible to synthesize. Relative energies of several low-lying singlets ( S n ${{S}_{n}}$ ) and triplets ( T n ${{T}_{n}}$ ), and their excitation nature (i. e., n π * ${n{\pi }^{^{\ast}}}$ or π π * ${\pi {\pi }^{^{\ast}}}$ ) and SOC are determined for these m ${m}$ S-HTGs in dichloromethane. Low-energy optical peak displays gradual red-shift with increasing thione content due to relatively smaller electronic gap resulted from greater degree of orbital delocalization. Significantly large SOC due to different orbital-symmetry and heavy-atom effect produces remarkably high ISC rates ( k I S C ${{k}_{ISC}}$ ~10 12  s -1 ) for enthalpically favoured S 1 n π * → T 2 ${{S}_{1}\left(n{\pi }^{^{\ast}}\right)\to {T}_{2}}$ ( π π * ${\pi {\pi }^{^{\ast}}}$ ) channel in these m ${m}$ S-HTGs, which outcompete radiative fluorescence rates (~10 8  s -1 ) even directly from higher lying optically bright π π * ${\pi {\pi }^{^{\ast}}}$ singlets. Importantly, high energy triplet excitons of ~1.7 eV resulting from such significantly large ISC rates from non-fluorescent S 1 n π * ${{S}_{1}\left(n{\pi }^{^{\ast}}\right)}$ make these thiocarbonylated HTGs ideal candidates for energy efficient triplet harvest including triplet-photosensitization.