title: Probing donor-acceptor interactions and co-conformational changes in redox active desymmetrized [2]catenanes.
abstract: We describe the synthesis and characterization of a series of desymmetrized donor-acceptor [2]catenanes where different donor and acceptor units are assembled within a confined catenated geometry. Remarkable translational selectivity is maintained in all cases, including two fully desymmetrized [2]catenanes where both donors and acceptors are different, as revealed by X-ray crystallography in the solid state, and by (1)H NMR spectroscopy and electrochemistry in solution. In all desymmetrized [2]catenanes the co-conformation is dominated by the strongest donor and acceptor pairs, whose charge-transfer interactions also determine the visible absorption properties. Voltammetric and spectroelectrochemical experiments show that the catenanes can be reversibly switched among as many as seven states, characterized by distinct electronic and optical properties, by electrochemical stimulation in a relatively narrow and easily accessible potential window. Moreover in some of these compounds the oxidation of the electron donor units or the reduction of the electron acceptor ones causes the circumrotation of one molecular ring with respect to the other. These features make these compounds appealing for the development of molecular electronic devices and mechanical machines.
authors.affiliation: The Molecular Foundry, Lawrence Berkeley National Laboratory, One Cyclotron Road, Berkeley, California 94720, USA.
authors.forename: Dennis
authors.initials: D
authors.lastname: Cao
authors.forename: Matteo
authors.initials: M
authors.lastname: Amelia
authors.forename: Liana M
authors.initials: LM
authors.lastname: Klivansky
authors.forename: Gayane
authors.initials: G
authors.lastname: Koshkakaryan
authors.forename: Saeed I
authors.initials: SI
authors.lastname: Khan
authors.forename: Monica
authors.initials: M
authors.lastname: Semeraro
authors.forename: Serena
authors.initials: S
authors.lastname: Silvi
authors.forename: Margherita
authors.initials: M
authors.lastname: Venturi
authors.forename: Alberto
authors.initials: A
authors.lastname: Credi
authors.forename: Yi
authors.initials: Y
authors.lastname: Liu