From Wires to Cables: Attempted Synthesis of 1,3,5-Trifluorenylcyclohexane as a Platform for Molecular Cables
American Chemical Society
Journal of Organic Chemisty
Original Item ID
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.
Talipov, Marat R.; Abdelwahed, Sameh H.; Thakur, Khushabu; Reid, Scott; and Rathore, Rajendra, "From Wires to Cables: Attempted Synthesis of 1,3,5-Trifluorenylcyclohexane as a Platform for Molecular Cables" (2016). Chemistry Faculty Research and Publications. 573.
Accepted version. Journal of Organic Chemistry, Vol 81, No. 4 (2016): pg. 1627-1634. DOI. © 2016 American Chemical Society, Used with permission.