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Tridecacyclene: A Cyclic Tetramer of Acenaphthylene
Author(s) -
Sumy Daniel P.,
Dodge Nicholas J.,
Harrison Chloe M.,
Finke Aaron D.,
Whalley Adam C.
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201600165
Subject(s) - tetramer , trimer , crystallography , molecule , chemistry , acenaphthylene , stacking , supramolecular chemistry , delocalized electron , ring (chemistry) , dication , planarity testing , stereochemistry , dimer , crystal structure , biochemistry , phenanthrene , organic chemistry , environmental chemistry , enzyme
In this manuscript, we describe the single‐step preparation of a cyclic tetramer of acenaphthylene through a Lewis acid‐catalyzed aldol cyclization of 1‐acenaphthenone. The previously unexplored cyclic tetramer material differs from the better‐known cyclic trimer, decacyclene, due to the presence of a central eight‐membered ring. This ring not only forces the molecule to distort significantly from planarity, but is also responsible for its unique electronic properties, including a decrease in the reduction potential (by about 0.4 eV) and optical gap (by about 0.73 eV), compared to the more planar decacyclene. The synthesized compound crystallizes into a unique packing structure with significant π‐stacking observed between adjacent molecules. Furthermore, due to its saddle‐like shape, the cyclic tetramer is able to form shape‐complementary interactions between its concave surface and the convex outer surface of buckminsterfullerene to generate cocrystalline supramolecular assemblies.