title: Donor- and/or acceptor-substituted expanded radialenes: theory, synthesis, and properties.
abstract: The synthesis of donor- (D) and/or acceptor (A)-expanded [4]radialenes has been developed on the basis of readily available dibromoolefin (7), tetraethynylethene (10 and 20), and vinyl triflate (12) building blocks. The successful formation of D/A radialenes relies especially on (1) effective use of a series alkynyl protecting groups, (2) Sonogashira cross-coupling reactions, and (3) the development of ring closing reactions to form the desired macrocyclic products. The expanded [4]radialene products have been investigated by spectroscopic (UV-vis absorption and emission) and quantum chemical computational methods (density functional theory and time dependent DFT). The combined use of theory and experiment provides a basis to evaluate the extent of D/A interactions via the cross-conjugated radialene framework as well as an interpretation of the origin of D/A interactions at an orbital level.
authors.affiliation: Department of Chemistry, University of Alberta , Edmonton, Alberta T6G 2G2, Canada.
authors.forename: Sharwatie
authors.initials: S
authors.lastname: Ramsaywack
authors.forename: Sila
authors.initials: S
authors.lastname: Karaca
authors.forename: Mojtaba
authors.initials: M
authors.lastname: Gholami
authors.forename: Adrian H
authors.initials: AH
authors.lastname: Murray
authors.forename: Frank
authors.initials: F
authors.lastname: Hampel
authors.forename: Robert
authors.initials: R
authors.lastname: McDonald
authors.forename: Nuran
authors.initials: N
authors.lastname: Elmaci
authors.forename: Hans Peter
authors.initials: HP
authors.lastname: Lüthi
authors.forename: Rik R
authors.initials: RR
authors.lastname: Tykwinski
mesh_terms: D000480:Alkynes / Q000737:chemistry*; D006840:Hydrocarbons, Alicyclic / Q000138:chemical synthesis* / Q000737:chemistry*; D006842:Hydrocarbons, Brominated / Q000737:chemistry*; D047028:Macrocyclic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D011789:Quantum Theory; D013056:Spectrophotometry, Ultraviolet
chemical_list: D000480:Alkynes; D006840:Hydrocarbons, Alicyclic; D006842:Hydrocarbons, Brominated; D047028:Macrocyclic Compounds