Cyclacene Stability: The Interplay of Strain, Aromaticity and Force Coupling
Ankit Somani, Divanshu Gupta, Jörg Grunenberg, Holger F. Bettinger
TL;DR
Cyclacene stability is mainly due to structural strain rather than aromaticity, resolving a long-standing debate.
Contribution
Demonstrates that ring strain, not aromaticity, primarily governs cyclacene thermodynamic stability.
Findings
Strain-corrected heats of hydrogenation show strain dominates cyclacene stability.
Even–odd aromaticity patterns do not translate into thermodynamic stabilization differences.
Aromatic contributions to cyclacene stability are negligible compared to strain effects.
Abstract
The energy of cyclacenes arises from a subtle interplay between structural strain and aromatic stabilization. To disentangle these effects, we employ strain‐corrected heats of hydrogenation as a direct thermodynamic probe, supported by thermally‐assisted‐occupation density functional theory that is capable of capturing strong static correlation. Previous analyses of magnetic properties demonstrated a pronounced even–odd pattern: cyclacenes with an even number of fused rings fulfill magnetic criteria of aromaticity, whereas odd‐membered analogs do not according to diamagnetic susceptibility exaltation, nucleus‐independent chemical shifts, and anisotropy of induced current density (ACID). Our results demonstrate, however, that this predicted aromaticity does not translate into discernible thermodynamic stabilization. Instead, cyclacene stability is dictated primarily by strain energy,…
Genes, proteins, chemicals, diseases, species, mutations and cell lines named across the full text — each resolved to its canonical identifier and authoritative record.
Click any figure to enlarge with its caption.
Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6
Figure 7
Figure 8
Figure 9
Figure 10
Figure 11
Figure 12
Figure 13
Figure 14
Figure 15
Figure 16Peer Reviews
No public reviews on file for this paper yet. If you reviewed it on a platform where reviews are public (OpenReview, ICLR, NeurIPS, ICML), you can paste yours below so the community can read it here.
Videos
No videos yet. Explain this paper in a talk, walkthrough, or lecture? Add one.
Taxonomy
TopicsSynthesis and Properties of Aromatic Compounds · Magnetism in coordination complexes · Organometallic Complex Synthesis and Catalysis