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.

The reductive aromatization of tridecacyclene

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Recently, we reported a one-step synthesis of tridecacyclene (1) -the cyclic tetramer of acenaphthylene. 12 The solid-state structure of 1 confirms that this molecule adopts a tub-like shape typical of COT-based molecules and exhibits clear bond alternation in its COT ring with the localized single and double bonds having bond lengths of 1.47 Å and 1.37 Å, respectively. Unlike previously explored systems, however, steric interactions between adjacent acenaphthylene units prevent the molecule from flattening, making it an ideal system to further the discussion between planarization and aromaticity in COT-based systems.Electrochemical studies (ESI, † Fig.

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Tridecacyclene Tetraimide: An Easily Reduced Cyclooctatetraene Derivative

“…Double bonds of the COT moiety are localized in the fivemembered rings (as shown in Scheme 1), as previously observed for the parent TC hydrocarbon. [34] Crystallographically determined average double and single bond lengths in the COT fragment of 3 a are 1.381(7) Å and 1.459(10) Å, respectively (cf. 1.369 Å and 1.470 Å reported for TC).…”

“…[27,28] Looking for a compact core motif that could be densely decorated with NMI units, we turned our attention to the hitherto unknown tridecacyclene tetraimide (TCTI, Figure 1), the higher homologue of DCTI. The parent tridecacyclene (TC), discovered in 2016 by Whalley et al, [34,35] can be reduced to the corresponding mono-and dianion at relatively low potentials, but its chemistry has remained relatively unexplored. While some π-extended TC derivatives are known, [36,18,37] functionalization of tridecacyclene has not been reported, possibly because of its unfavorable reactivity, e.g.…”

Combinatorial design of molecular seeds for chirality-controlled synthesis of single-walled carbon nanotubes

“…Finally, we have performed aldol cyclotetramerization of ketones to demonstrate the general feasibility of our strategy. The cyclotetramerization was carried out in a ODCB/TiCl 4 mixture specially optimized for the tetramer formation 53 . However, the reaction cannot be shifted completely to the tetramer formation and it is always accompanied by the formation of trimers.…”