In:
Advanced Materials, Wiley, Vol. 32, No. 32 ( 2020-08)
Abstract:
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•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⊂ExBox 4+ supramolecular dyad. The TBP⊂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⊂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⊂ExBox 4+ for the population of the low‐lying T 1 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.
Type of Medium:
Online Resource
ISSN:
0935-9648
,
1521-4095
DOI:
10.1002/adma.202001592
Language:
English
Publisher:
Wiley
Publication Date:
2020
detail.hit.zdb_id:
1474949-X
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