Document Type

Article

Language

eng

Publication Date

2016

Publisher

American Chemical Society

Source Publication

Journal of Organic Chemisty

Source ISSN

0022-3263

Original Item ID

DOI: 10.1021/acs.joc.5b02792

Abstract

Multiple molecular wires braided together in a single assembly, termed as molecular cable, are promising next-generation materials for effective long-range charge transport. As an example of the platform for constructing molecular cables, 1,3,5-trifluorenylcyclohexane (TFC) and its difluorenyl analogues (DFCs) were systematically investigated both experimentally (X-ray crystallography) and theoretically (DFT calculations). Although the syntheses of DFCs were successfully achieved, the synthesis of TFC, which involved a similar intramolecular Friedel–Crafts cyclization as the last step, was unsuccessful. An exhaustive study of the conformational landscape of cyclohexane ring of TFC and DFCs revealed that TFC is a moderately strained molecule (∼17 kcal/mol), and computational studies of the reaction profile show that this steric strain, present in the transition state, is responsible for the unusually high (∼5 years) reaction half-life. A successful synthesis of TFC will require that the steric strain is introduced in multiple steps, and such alternative strategies are being currently explored.

Comments

Accepted version. Journal of Organic Chemistry, Vol 81, No. 4 (2016): pg. 1627-1634. DOI. © 2016 American Chemical Society, Used with permission.

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