title: Tridecacyclene: A Cyclic Tetramer of Acenaphthylene.
abstract: 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.
authors.affiliation: Department of Chemistry, University of Vermont, Burlington, Vermont, 05405, USA.
authors.forename: Daniel P
authors.initials: DP
authors.lastname: Sumy
authors.affiliation: Department of Chemistry, University of Vermont, Burlington, Vermont, 05405, USA.
authors.forename: Nicholas J
authors.initials: NJ
authors.lastname: Dodge
authors.affiliation: Department of Chemistry, University of Vermont, Burlington, Vermont, 05405, USA.
authors.forename: Chloe M
authors.initials: CM
authors.lastname: Harrison
authors.affiliation: Swiss Light Source, Paul Scherrer Institute, 5232, Villigen PSI, Switzerland.
authors.forename: Aaron D
authors.initials: AD
authors.lastname: Finke
authors.affiliation: Department of Chemistry, University of Vermont, Burlington, Vermont, 05405, USA. Adam.Whalley@uvm.edu.
authors.forename: Adam C
authors.identifier: http://orcid.org/0000-0002-1587-0143
authors.initials: AC
authors.lastname: Whalley
mesh_terms: D000073:Acenaphthenes / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D003500:Cyclization; D058116:Lewis Acids / Q000737:chemistry*; D015394:Molecular Structure
chemical_list: D000073:Acenaphthenes; D058116:Lewis Acids; C000609598:tridecacyclene; C042553:acenaphthylene
keywords: Lewis acids; arenes; buckminsterfullerene; polycyclic aromatic hydrocarbons; supramolecular chemistry