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Design and synthesis of the first triply twisted Möbius annulene



As long as 50 years ago theoretical calculations predicted that Möbius annulenes with only one π surface and one edge would exhibit peculiar electronic properties and violate the Hückel rules. Numerous synthetic attempts notwithstanding, the first singly twisted Möbius annulene was not prepared until 2003. Here we present a general, rational strategy to synthesize triply or even more highly twisted cyclic π systems. We apply this strategy to the preparation of a triply twisted [24]dehydroannulene, the structure of which was confirmed by X-ray analysis. Our strategy is based on the topological transformation of ‘twist’ into ‘writhe’. The advantage is twofold: the product exhibits a lower degree of strain and precursors can be designed that inherently include the writhe, which, after cyclization, ends up in the Möbius product. With our strategy, triply twisted systems are easier to prepare than their singly twisted counterparts.

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Figure 1: Strategies to introduce multiple twists in a cycle.
Figure 2: Combining building blocks with writhe to produce a triply twisted system and identification of a target structure.
Figure 3: Synthesis of the Möbius dehydroannulene.
Figure 4: Structure of the Möbius dehydroannulene 1a/b with Lk = 3 as determined by X-ray crystallography.
Figure 5: Topological procedure to determine the linking number Lk of the π system of 1.


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We acknowledge The Academy of Finland (K.R., project no. 263256 and 265328) and the National Doctoral Program in Nanoscience, Finland (F.T., PhD Fellowship) for financial support. K.R. and F.T. thank G. Schaller and L. Kaufmann (Freie Universität Berlin, Germany) for performing some preliminary crystallization experiments.

Author information




G.R.S. worked out the topological construction strategy, developed the syntheses, carried out the experiments and characterized the compounds. R.H. developed the topological strategy and directed the study. F.T. prepared the single crystals, collected the data and solved and refined the structure together with K.R. K.R. supervised the X-ray diffraction part of the work. Y.O. and J.S. performed the separation and CD measurement of the enantiomers. G.R.S., R.H., F.T. and K.R. wrote the manuscript.

Corresponding authors

Correspondence to Kari Rissanen or Rainer Herges.

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The authors declare no competing financial interests.

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Crystallographic data for racemic compound 1 (CIF 627 kb)

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Schaller, G., Topić, F., Rissanen, K. et al. Design and synthesis of the first triply twisted Möbius annulene. Nature Chem 6, 608–613 (2014).

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