TY  - JOUR
AU  - Sukumaran, Divya P.
AU  - Shoyama, Kazutaka
AU  - Dubey, Rajeev K.
AU  - Wuerthner, Frank
TI  - Cooperative Binding and Chirogenesis in an Expanded Perylene Bisimide Cyclophane
JO  - Journal of the American Chemical Society
VL  - 146
IS  - 31
SN  - 0002-7863
CY  - Washington, DC
PB  - ACS Publications
M1  - PUBDB-2024-06122
SP  - 22077-22084
PY  - 2024
AB  - The encapsulation of more than one guest molecule into a synthetic cavity is a highly desirable yet a highly challenging task to achieve for neutral supramolecular hosts in organic media. Herein, we report a neutral perylene bisimide cyclophane, which has a tailored chiral cavity with an interchromophoric distance of 11.2 Å, capable of binding two aromatic guests in a π-stacked fashion. Detailed host–guest binding studies with a series of aromatic guests revealed that the encapsulation of the second guest in this cyclophane is notably more favored than the first one. Accordingly, for the encapsulation of the coronene dimer, a cooperativity factor (α) as high as 485 was observed, which is remarkably high for neutral host–guest systems. Furthermore, a successful chirality transfer, from the chiral host to encapsulated coronenes, resulted in a chiral charge-transfer (CT) complex and the rare observation of circularly polarized emission originating from the CT state for a noncovalent donor–acceptor assembly in solution. The involvement of the CT state also afforded an enhancement in the luminescence dissymmetry factor (glum) value due to its relatively large magnetic transition dipole moment. The 1:2 binding pattern and chirality-transfer were unambiguously verified by single-crystal X-ray diffraction analysis of the host–guest superstructures. 
LB  - PUB:(DE-HGF)16
C6  - pmid:39045838
UR  - <Go to ISI:>//WOS:001276202900001
DO  - DOI:10.1021/jacs.4c08073
UR  - https://bib-pubdb1.desy.de/record/615367
ER  -