@article{7d6d24744b8a42f9877ecde127b7ef8e,
title = "Supramolecular Porous Organic Nanocomposites for Heterogeneous Photocatalysis of a Sulfur Mustard Simulant",
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 (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.",
keywords = "cyclophanes, nanocomposites, photocatalysis, photosensitizers, polymers",
author = "Yassine Beldjoudi and Ahmet Atilgan and Weber, {Jacob A.} and Indranil Roy and Young, {Ryan M.} and Jierui Yu and Pravas Deria and Enciso, {Alan E.} and Wasielewski, {Michael R.} and Hupp, {Joseph T.} and Stoddart, {J. Fraser}",
note = "Funding Information: Y.B. and A.A. contributed equally to this work. The authors thank Northwestern University (NU) for their generous support of this research. The authors thank the personnel in the Integrated Molecular Structure Education and Research Center (IMSERC) at NU for their assistance in the collection of the data. This project was also supported by the Defense Threat Reduction Agency under grant number HDTRA1‐19‐1‐0010 (J.T.H.). P.D. thanks Southern Illinois University ‐ Carbondale (SIUC) for start up support. It was also supported in the Wasielewski laboratory by the National Science Foundation under grant number DMR‐1710104 (M.R.W.). Funding Information: Y.B. and A.A. contributed equally to this work. The authors thank Northwestern University (NU) for their generous support of this research. The authors thank the personnel in the Integrated Molecular Structure Education and Research Center (IMSERC) at NU for their assistance in the collection of the data. This project was also supported by the Defense Threat Reduction Agency under grant number HDTRA1-19-1-0010 (J.T.H.). P.D. thanks Southern Illinois University - Carbondale (SIUC) for start up support. It was also supported in the Wasielewski laboratory by the National Science Foundation under grant number DMR-1710104 (M.R.W.). Note: Citations to Table 2 and 3 on page 8 in the paragraph beginning ?The singlet and triplet excited states?? were corrected on August 11, 2020, after initial publication online. Publisher Copyright: {\textcopyright} 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim",
year = "2020",
month = aug,
day = "1",
doi = "10.1002/adma.202001592",
language = "English (US)",
volume = "32",
journal = "Advanced Materials",
issn = "0935-9648",
publisher = "Wiley-VCH Verlag",
number = "32",
}