title: From Wires to Cables: Attempted Synthesis of 1,3,5-Trifluorenylcyclohexane as a Platform for Molecular Cables.
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.
authors.affiliation: Department of Chemistry, Marquette University , P.O. Box 1881, Milwaukee, Wisconsin 53201-1881, United States.
authors.forename: Marat R
authors.initials: MR
authors.lastname: Talipov
authors.affiliation: Department of Chemistry, Marquette University , P.O. Box 1881, Milwaukee, Wisconsin 53201-1881, United States.
authors.forename: Sameh H
authors.initials: SH
authors.lastname: Abdelwahed
authors.affiliation: Department of Chemistry, Marquette University , P.O. Box 1881, Milwaukee, Wisconsin 53201-1881, United States.
authors.forename: Khushabu
authors.initials: K
authors.lastname: Thakur
authors.affiliation: Department of Chemistry, Marquette University , P.O. Box 1881, Milwaukee, Wisconsin 53201-1881, United States.
authors.forename: Scott A
authors.initials: SA
authors.lastname: Reid
authors.affiliation: Department of Chemistry, Marquette University , P.O. Box 1881, Milwaukee, Wisconsin 53201-1881, United States.
authors.forename: Rajendra
authors.initials: R
authors.lastname: Rathore
mesh_terms: D018360:Crystallography, X-Ray; D005464:Fluorobenzenes / Q000138:chemical synthesis* / Q000737:chemistry; D008958:Models, Molecular; D008968:Molecular Conformation
chemical_list: D005464:Fluorobenzenes; C519635:1,3,5-trifluorobenzene