Transient spectroscopy revealed fluorescence, TADF, phosphorescence, and LPL (Figs. 3g,h, Extended Data Fig. ). Since the donor molecules have a partial intramolecular CT nature (Supplementary Information 4.12.1), they exhibited weak intramolecular, similar to the behaviour of DAAPC/PMMA. To avoid confusion with the TADF of the intermolecular CT ( 3 CT or LED to 1 CT), we present the TADF of the donor as a transition from the lowest energy triplet LE state ( 3 LED) to the relative singlet LE state ( 1 LED). The 3 LED to LED intramolecular TADF and the 3 CT or LED to CT intermolecular TADF can be distinguished from the excitation-duration-dependence of emission intensity because the intramolecular TADF is independent of excitation duration, whereas LPL is observed together with the intermolecular TADF by charge separation at longer excitation duration (Fig. , Extended Data Fig. ). In the large ΔELUMO system such as DAAPC/3,7-PPT, the 1 CT emission and the 3 CT to CT intermolecular TADF were dominant (Fig. ). In the middle ΔELUMO system such as DAAPC/2,8-PPT, the 1 CT emission and the 3 LED to 1 CT intermolecular TADF were dominant processes. In the small ΔELUMO system such as DAAPC/2-PPT, the 3 LED to 1 LED intramolecular TADF was dominant instead of the 3 LED to 1 CT intermolecular TADF. This suggests that the 3 LED exciton is transferred to LED instead of CT when ΔELUMO is small, meaning ΔELE-CT is small. In contrast, although DAAPC/2-PPT showed a small spectral shift from DAAPC/PMMA, which did not form intermolecular CT (Fig. ), the clear CT emission at 100-300 ns (Extended Data Fig. ) and LPL at longer excitation duration (Fig. ) confirmed CT formation. The 3 LED to 1 LED intramolecular TADF of DAAPC/2-PPT was stronger than that of DAAPC/PMMA, suggesting an enhancement in intersystem crossing and reverse intersystem crossing facilitated by the intermolecular CT excited state . DAAPC/2-PPT has a very small ΔELUMO, but the LPL is also influenced by the thermal stability of the host phase , and 2-PPT, which has a lower glass transition temperature, exhibited a much weaker LPL than the DAAPC/2,8-PPT. Because the overlap between the absorption of the charge-separated states and the LPL spectra caused self-absorption in LPL, the 4,6-PPT and 3,7-PPT systems exhibited shorter LPL durations (Extended Data Fig. ).