促进三重态的产生对于开发高效的光催化体系至关重要。这项研究提出了一种通过共价和非共价方法组合的宿主稳定的通过空间缀合的新方法。设计的积木,4,4'-(1,4(1,4)-二苯环己烷-1,4-二基)双(1-苯基吡啶)氯化物,具有固有稳定的贯穿空间共轭。当这个块形成一个1:1的主客复合体与葫芦[8]uril时,通过空间的共轭进一步稳定在封闭的腔内。三重态的产生和寿命都显著增加,由宿主稳定的通过空间缀合产生。此外,6.58×1014M-1的超高结合常数确保了宿主稳定作用的持久性。因此,主客体络合物在硫醚和芳族醇的光催化氧化中充当高效催化剂。在木质素的光降解中,复杂的天然产物,主客综合体也表现出很高的效率,展示其稳健性。该研究有望丰富超分子光化学的工具箱,并为制造高效的超分子光催化剂提供策略。
Promoting the generation of triplet states is essential for developing efficient photocatalytic systems. This research presents a novel approach of host-stabilized through-space conjugation via the combination of covalent and non-covalent methods. The designed building block, 4,4\'-(1,4(1,4)-dibenzene cyclohexaphane-1,4-diyl)bis(1-phenylpyridinium) chloride, features inherently stable through-space conjugation. When this block forms a 1:1 host-guest complex with cucurbit[8]uril, the through-space conjugation is further stabilized within the confined cavity. Both the generation and lifetime of triplet state are significantly increased, resulting from the host-stabilized through-space conjugation. Additionally, the ultrahigh binding constant of 6.58 × 1014 M-1 ensures the persistence of host-stabilization effect. As a result, the host-guest complex acts as a highly efficient catalyst in the photocatalytic oxidation of thioether and aromatic alcohol. In the photodegradation of lignin, a complex natural product, the host-guest complex also exhibits high efficiency, demonstrating its robustness. This line of research is anticipated to enrich the toolbox of supramolecular photochemistry and provide a strategy for fabricating efficient supramolecular photocatalysts.