To gain further insight into the excited state characteristics, we perform single-point excited state analysis by time-dependent (TD-)DFT on the M062X-GD3/def2-TZVP level of theory in the gas phase and we analyze the natural transition orbitals (NTO) of the S1 geometry (see Figure ). For PyFlCz we observe a distinct LE state in the gas phase, as the respective holes and electrons reside on the same subunit of the molecule (see Figure ). This observation corresponds well with our experimental Lippert-Mataga plots, where we observe only marginal change in slope. In PyPhCz, the carbazole unit hosts part of the hole, while the pyrene hosts both hole and electron.