The calculated lowest energy gap (ΔES1-T2) for TPE-Py and TPE-Qu was found to be 0.16 and 0.11 eV, respectively, which facilitated the promotion of intersystem crossing (ISC) to a triplet state. Meanwhile, spin-orbit coupling (SOC) played a crucial role in efficient ISC process. The calculated SOC value of 1.46 cm -1 between S2 and T2 for TPE-Py indicates the potential for a more efficient ISC process from S2 to T2. While, TPE-Qu showed a relatively small SOC in contrast to TPE-Py. The photophysical properties of TPE-Py, TPE-Qu and their supramolecular complexes were initially investigated by using UV-vis and photoluminescence (PL) spectra. As presented in the absorption spectra, the main band of TPE-Py and TPE-Qu were centered at 495 and 520 nm in DMSO (1.0 × 10 -5 M), respectively (Figure and Figure ). A smaller peak at 330 nm was attributed to TPE unit in their structures. When 1.0 equivalent of α-CD was added in the solution of TPE-Py, the main absorption peak at 495 was reduced, while the absorption band at 330 nm enhanced obviously, indicating emerging efficient interactions between TPE-Py and α-CD. For TPE-Qu, neglected change was attained after interaction with α-CD in absorption profile, and the PL spectra showed a little enhancement, demonstrating they had minor intermolecular interactions (Figure ). Upon excitation at 490 and 520 nm, the PL spectra of TPE-Py and TPE-Qu showed a maximum peak at 610 and 638 nm in DMSO, respectively (Figure ). Given the strong interactions between host and guests from the absorption and fluorescence profiles, we selected the TPE-Py and α-CD system for the next biological experiment. Their AIE behaviors were explored in The efficiency of ROS generation is a critical factor in evaluating the ability of PDT. The overall capability of ROS production was assessed by using the 2,7dichlorodihydrofluorescein (DCFH-DA) indicator under white light. DCFH-DA emitted weakly fluorescence under irradiation. However, the fluorescence intensity experienced a significant 67-fold increase after 20 seconds of illumination, demonstrating rapid and efficient ROS generation (Figure and Figure ). After forming a complex with α-CD, the efficiency of ROS generation was partially decreased. Then, TPE-Qu and their supramolecular assemblies were also measured under same condition. As illustrated in Figure , its fluorescence intensity was quickly enhanced with a 30-fold. Nevertheless, its capacity for ROS production is inferior to that of TPE-Py. Upon interaction with α-CD, their assemblies also showed minor decrease in PL intensity. In order to identify the specific species of ROS, dihydrorhodamine 123 (DHR123) as type I ROS indicator was employed for the detection of radical O2 •-. As shown in Figure and Figure , the mixture of DHR123 and TPE-Py or TPE-Qu all afforded a distinct enhancement in PL intensity, proving they can generate efficient type I ROS. Upon addition of α-CD, there was a small decrease in O2 •- generation efficiency. Then, 9,10-anthracenediyl-bis(methylene)-dimalonic acid (ABDA) was employed for the detection of type II ROS 1 O2 by utilizing absorption spectra (Figure and Figure ). TPE-Py and TPE-Qu also can generate type II ROS with a 40% and 30% of ABDA consumption, respectively. It was worth noting that the supramolecular complexes TPE-Pyα-CD drastically accelerated 1 O2 generation, which can aggravate cellular hypoxia and promote the release of hypoxia-activated prodrugs.