CC BY-NC-ND 4.0 · Organic Materials 2020; 02(04): 323-329
DOI: 10.1055/s-0040-1721102
Focus Issue: Curved Organic π-Systems
Original Article

Easier to Twist than Bend: The Scope of the Bridge Formation Approach to Naphthalenophane Synthesis

a  Institute of Chemistry, The Hebrew University of Jerusalem, Edmond J. Safra Campus, Jerusalem, Israel
,
b  Chemical Research Support Unit, Weizmann Institute of Science, Rehovot, Israel
,
a  Institute of Chemistry, The Hebrew University of Jerusalem, Edmond J. Safra Campus, Jerusalem, Israel
,
a  Institute of Chemistry, The Hebrew University of Jerusalem, Edmond J. Safra Campus, Jerusalem, Israel
› Author Affiliations
Funding Information This research was supported by the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation program (Grant Agreement No. 850836, ERC Starting Grant “PolyHelix”). A.B. is supported by a PBC fellowship.


Abstract

Twisting anthracene and higher acenes can alter their optical, magnetic, and electronic properties. To test the effect of twisting on the lower homologue, naphthalene, we synthesized tethered naphthalenophanes bearing alkyl bridges. Both X-ray structure and DFT calculations show that hexyl and butyl bridges induce a 6° and 12° end-to-end twist on the naphthalene unit, respectively. Attempts to increase the twisting further using shorter tethers resulted in an elimination product. Enantiomerically pure naphthalenophanes display strong chiroptical properties, which intensify with increasing twist. Attempts to induce bending, rather than twisting, using the same synthetic methodology, resulted in intermolecular dimerization, yielding macrocyclic naphthalenes. This work highlights the importance of steric hindrance in the synthesis of curved cyclophanes using the bridge formation approach.

Supporting Information

Supporting Information for this article is available online at http://doi.org/10.1055/s-0040-1721102.


Supporting Information



Publication History

Received: 08 September 2020

Accepted: 12 October 2020

Publication Date:
14 December 2020 (online)

© 2020. The Author(s). This is an open access article published by Thieme under the terms of the Creative Commons Attribution-NonDerivative-NonCommercial License, permitting copying and reproduction so long as the original work is given appropriate credit. Contents may not be used for commercial purposes, or adapted, remixed, transformed or built upon. (https://creativecommons.org/licenses/by-nc-nd/4.0/)

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