Supramolecular Porous Organic Nanocomposites for Heterogeneous Photocatalysis of a Sulfur Mustard Simulant
Supramolecular Porous Organic Nanocomposites for Heterogeneous Photocatalysis of a Sulfur Mustard Simulant
复制标题
DOI：
10.1002/adma.202001592
复制
发表时间：
2020-06-29
影响因子：
29.4
通讯作者：
Stoddart, J. Fraser
中科院分区：
文献类型：
--
作者：
Beldjoudi, Yassine;Atilgan, Ahmet;Stoddart, J. Fraser
高效的异质光敏材料需要大的可及表面积和合适能量的激子，并具有明确的自旋结构。将四阳离子环蕃（ExBox（4+））限制在无孔阴离子聚苯乙烯磺酸盐（PSS）基质中，可使ExBox中心点PSS的表面积增加高达225 m2 g-1。通过结合1，3，5，8-四溴芘（TBP）中Br重原子的自旋-轨道耦合和ExBox（4+）超分子二联体中TBP子集的光诱导电子转移，实现了有效的系间交叉. ExBox（4+）络合物的TBP子集在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。最低的三重态（T-1，1.89 eV）位于TBP上，并且在能量上与电荷分离态（CT，2.14 eV）接近。ExBox（4+）的TBP子集的均相和非均相光催化活性，对于消除硫芥模拟物，已被证明比TBP和ExBox（+4）显著更有效，证实了ExBox（4+）的TBP子集中新形成的激发态流形对于低位T（1）态的布居的重要性。ExBox中心点PSS纳米复合材料的TBP子集的高稳定性、易于制备和高性能预示着使用主客体化学的新型超分子非均相光敏剂的未来发展。
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 (ExBox(4+)) within a nonporous anionic polystyrene sulfonate (PSS) matrix leads to a surface area increase of up to 225 m(2)g(-1)in ExBox center dot 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 subset of ExBox(4+)supramolecular dyad. The TBP subset of ExBox(4+)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 (T-1, 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 subset of ExBox(4+), 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 subset of ExBox(4+)for the population of the low-lying T(1)state. The high stability, facile preparation, and high performance of the TBP subset of ExBox center dot PSS nanocomposites augur well for the future development of new supramolecular heterogeneous photosensitizers using host-guest chemistry.