title: Metal nitride cluster fullerene M3N@C80 (M=Y, Sc) based dyads: synthesis, and electrochemical, theoretical and photophysical studies.
abstract: The first pyrrolidine and cyclopropane derivatives of the trimetallic nitride templated (TNT) endohedral metallofullerenes I(h)-Sc(3)N@C(80) and I(h)-Y(3)N@C(80) connected to an electron-donor unit (i.e., tetrathiafulvalene, phthalocyanine or ferrocene) were successfully prepared by 1,3-dipolar cycloaddition reactions of azomethine ylides and Bingel-Hirsch-type reactions. Electrochemical studies confirmed the formation of the [6,6] regioisomers for the Y(3)N@C(80)-based dyads and the [5,6] regioisomers in the case of Sc(3)N@C(80)-based dyads. Similar to other TNT endohedral metallofullerene systems previously synthesized, irreversible reductive behavior was observed for the [6,6]-Y(3)N@C(80)-based dyads, whereas the [5,6]-Sc(3)N@C(80)-based dyads exhibited reversible reductive electrochemistry. Density functional calculations were also carried out on these dyads confirming the importance of these structures as electron transfer model systems. Furthermore, photophysical investigations on a ferrocenyl-Sc(3)N@C(80)-fulleropyrrolidine dyad demonstrated the existence of a photoinduced electron-transfer process that yields a radical ion pair with a lifetime three times longer than that obtained for the analogous C(60) dyad.
authors.affiliation: Department of Chemistry, Clemson University, 219 Hunter Laboratories, Clemson, SC 29634, USA.
authors.forename: Julio R
authors.initials: JR
authors.lastname: Pinzón
authors.forename: Claudia M
authors.initials: CM
authors.lastname: Cardona
authors.forename: Maria Angeles
authors.initials: MA
authors.lastname: Herranz
authors.forename: Marta E
authors.initials: ME
authors.lastname: Plonska-Brzezinska
authors.forename: Amit
authors.initials: A
authors.lastname: Palkar
authors.forename: Andreas J
authors.initials: AJ
authors.lastname: Athans
authors.forename: Nazario
authors.initials: N
authors.lastname: Martín
authors.forename: Antonio
authors.initials: A
authors.lastname: Rodríguez-Fortea
authors.forename: Josep M
authors.initials: JM
authors.lastname: Poblet
authors.forename: Giovanni
authors.initials: G
authors.lastname: Bottari
authors.forename: Tomás
authors.initials: T
authors.lastname: Torres
authors.forename: S Shankara
authors.initials: SS
authors.lastname: Gayathri
authors.forename: Dirk M
authors.initials: DM
authors.lastname: Guldi
authors.forename: Luis
authors.initials: L
authors.lastname: Echegoyen
mesh_terms: D000465:Algorithms; D004563:Electrochemistry; D037741:Fullerenes / Q000737:chemistry* / Q000528:radiation effects; D037742:Nanotubes, Carbon; D012538:Scandium / Q000737:chemistry*; D019032:Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization; D015019:Yttrium / Q000737:chemistry*
chemical_list: D037741:Fullerenes; D037742:Nanotubes, Carbon; D015019:Yttrium; D012538:Scandium