An innovative design strategy of placing sulfur (S)-atoms within the pendant functional groups and at carbonyl positions in conventional perylenimide (PNI-O) has been demonstrated to investigate the condensed state structure–property relationship and potential photodynamic therapy (PDT) application. Incorporation of simply S-atoms at the peri-functionalized perylenimide (RPNI-O) leads to an aggregation-induced enhanced emission luminogen (AIEEgen), 2-hexyl-8-(thianthren-1-yl)-1H-benzo[5,10]anthra[2,1,9-def]isoquinoline-1,3(2H)-dione (API), which achieves a remarkable photoluminescence quantum yield (Φ_PL) of 0.85 in aqueous environments and established novel AIE mechanisms. Additionally, substitution of the S-atom at the carbonyl position in RPNI-O leads to thioperylenimides (RPNI-S): 2-hexyl-8-phenyl-1H-benzo[5,10]anthra[2,1,9-def]isoquinoline-1,3(2H)-dithione (PPIS), 8-([2,2′-bithiophen]-5-yl)-2-hexyl-1H-benzo[5,10]anthra[2,1,9-def]isoquinoline-1,3(2H)-dithione (THPIS), and 2-hexyl-8-(thianthren-1-yl)-1H-benzo[5,10]anthra[2,1,9-def]isoquinoline-1,3(2H)-dithion (APIS), with distinct photophysical properties (enlarged spin–orbit coupling (SOC) and Φ_PL ≈ 0.00), and developed diverse potent photosensitizers (PSs). The present work provides a novel SOC enhancement mechanism via pronounced H-aggregation. Surprisingly, the lowest singlet oxygen quantum yield (Φ_Δ) and theoretical calculation suggest the specific type-I PDT for RPNI-S. Interestingly, RPNI-S efficiently produces superoxide (O₂˙⁻) due to its remarkably lower Gibbs free energy (ΔG) values (THPIS: −40.83 kcal mol⁻¹). The non-toxic and heavy-atom free very specific thio-based PPIS and THPIS PSs showed selective and efficient PDT under normoxia, as a rare example.

中文翻译：

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苝酰亚胺中的硫原子位置工程：结构-性质关系和 H 聚集定向 I 型光动力疗法


将硫（S）原子放置在传统苝酰亚胺（PNI-O）的侧链官能团内和羰基位置的创新设计策略已被证明可以研究凝聚态结构-性能关系和潜在的光动力疗法（PDT）应用。在功能化苝酰亚胺 (RPNI-O) 上简单掺入 S 原子会产生聚集诱导增强发射发光体 (AIEEgen)，2-己基-8-(thianthren-1-yl)-1H-苯并[5， 10]anthra[2,1,9-def]isoquinoline-1,3(2H)-dione (API)，在水环境中实现了 0.85 的显着光致发光量子产率 (Φ _PL )，并建立了新颖的 AIE 机制。此外，RPNI-O 中羰基位置的 S 原子被取代，得到硫代苝酰亚胺 (RPNI-S)：2-己基-8-苯基-1H-苯并[5,10]蒽[2,1,9-def ]异喹啉-1,3(2H)-二硫酮 (PPIS), 8-([2,2'-联噻吩]-5-基)-2-己基-1H-苯并[5,10]蒽[2,1, 9-def]异喹啉-1,3(2H)-二硫酮 (THPIS) 和 2-己基-8-(thianthren-1-yl)-1H-苯并[5,10]蒽[2,1,9-def ]isoquinoline-1,3(2H)-dithion (APIS)，具有独特的光物理性质（扩大的自旋轨道耦合（SOC）和Φ _PL ≈ 0.00），并开发了多种有效的光敏剂（PSs）。目前的工作通过明显的 H 聚集提供了一种新颖的 SOC 增强机制。令人惊讶的是，最低的单线态氧量子产率（Φ _Δ ）和理论计算表明 RPNI-S 具有特定的 I 型 PDT。有趣的是，RPNI-S 因其显着较低的吉布斯自由能 (ΔG) 值（THPIS：-40.83 kcal mol ⁻¹