Efficient heterogeneous photosensitizing materials require both large accessible surface areas and excitons of suitable energies and with well‐defined spin structures. Confinement of the tetracationic cyclophane (ExBox⁴⁺) within a nonporous anionic polystyrene sulfonate (PSS) matrix leads to a surface area increase of up to 225 m² g⁻¹ in ExBox•PSS. Efficient intersystem crossing is achieved by combining the spin‐orbit coupling associated to Br heavy atoms in 1,3,5,8‐tetrabromopyrene (TBP), and the photoinduced electron transfer in a TBP⊂ExBox⁴⁺ supramolecular dyad. The TBP⊂ExBox⁴⁺ complex displays a charge transfer band at 450 nm and an exciplex emission at 520 nm, indicating the formation of new mixed‐electronic states. The lowest triplet state (T₁, 1.89 eV) is localized on the TBP and is close in energy with the charge separated state (CT, 2.14 eV). The homogeneous and heterogeneous photocatalytic activities of the TBP⊂ExBox⁴⁺, for the elimination of a sulfur mustard simulant, has proved to be significantly more efficient than TBP and ExBox⁺⁴, confirming the importance of the newly formed excited‐state manifold in TBP⊂ExBox⁴⁺ for the population of the low‐lying T₁ state. The high stability, facile preparation, and high performance of the TBP⊂ExBox•PSS nanocomposites augur well for the future development of new supramolecular heterogeneous photosensitizers using host–guest chemistry.

中文翻译：

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超分子多孔有机纳米复合材料对芥菜油模拟物的非均相光催化作用。

高效的异质光敏材料既需要较大的可及表面积，又需要具有适当能量且具有明确自旋结构的激子。在无孔阴离子聚苯乙烯磺酸盐（PSS）基质内限制四阳离子环烷（ExBox ⁴⁺）可使ExBox•PSS的表面积增加多达225 m ² g ^-1。通过结合与1,3,5,8-四溴py（TBP）中的Br重原子相关的自旋轨道耦合以及在TBP⊂ExBox4 ⁺超分子二倍体中的光诱导电子转移，可以实现有效的系统间交叉。TBP⊂ExBox4 ⁺配合物在450 nm处显示电荷转移带，在520 nm处显示激基复合物发射，表明形成了新的混合电子态。最低三重态（T ₁，1.89 eV）的被定位在TBP和接近在能量与电荷分离状态（CT，2.14伏特）。事实证明，TBP⊂ExBox4 ⁺的均相和非均相光催化活性对于消除芥子气模拟物的效率明显高于TBP和ExBox ⁺⁴，这证实了新形成的激发态歧管在TBP中的重要性⊂ExBox4 ⁺用于低层T ₁的人口州。TBP⊂ExBox•PSS纳米复合物的高稳定性，易制备性和高性能很好地预示了未来使用宿主-客体化学方法开发的新型超分子异质光敏剂的前景。