title: Weak distance dependence of through-bond interactions in tetrahydro-4H-thiopyran-4-ylidene end-capped oligo(cyclohexylidenes); a computational survey.
abstract: Calculations on members of the oligo(cyclohexylidene) series [(n), n = 1-5)] and related tetrahydro-4H-thiopyran end-capped analogues [(n), n = 1-4)] show a strong through-bond coupling between their pi bonds and sulfur lone pairs (Lp(pi)S). This coupling is mediated by an interaction between the H(ax)-C-C-H(ax) structural sub-units and the pi bonds connecting the cyclohexyl moieties. A comparison of the length dependency of the through-bond coupling via an oligo(cyclohexylidene) and an alkane bridge [divinyl alkanes (n)] shows that oligo(cyclohexylidenes) are more efficient in mediating through-bond couplings over large distances. Oligo(cyclohexylidene) bridges exhibit molecular wire characteristics.
authors.affiliation: Theoretical Chemistry Group, Utrecht University, Padualaan 8, Utrecht, The Netherlands.
authors.forename: Remco W A
authors.initials: RW
authors.lastname: Havenith
authors.forename: Cornelis A
authors.initials: CA
authors.lastname: van Walree
authors.forename: Alwin W
authors.initials: AW
authors.lastname: Marsman
authors.forename: Joop H
authors.initials: JH
authors.lastname: van Lenthe
authors.forename: Leonardus W
authors.initials: LW
authors.lastname: Jenneskens
mesh_terms: D003198:Computer Simulation; D004735:Energy Transfer; D006838:Hydrocarbons / Q000737:chemistry; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D008956:Models, Chemical; D008958:Models, Molecular; D008968:Molecular Conformation; D011720:Pyrazoles / Q000737:chemistry*
chemical_list: D006838:Hydrocarbons; D011720:Pyrazoles; C030011:carbene; C002626:thiopyrine; D008697:Methane