Metal nitride cluster fullerene M3N@C80 (M=Y, Sc) based dyads: synthesis, and electrochemical, theoretical and photophysical studies.
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.
Pinzón
Julio R
JR
Department of Chemistry, Clemson University, 219 Hunter Laboratories, Clemson, SC 29634, USA.
Cardona
Claudia M
CM
Herranz
Maria Angeles
MA
Plonska-Brzezinska
Marta E
ME
Palkar
Amit
A
Athans
Andreas J
AJ
Martín
Nazario
N
Rodríguez-Fortea
Antonio
A
Poblet
Josep M
JM
Bottari
Giovanni
G
Torres
Tomás
T
Gayathri
S Shankara
SS
Guldi
Dirk M
DM
Echegoyen
Luis
L
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*
D037741:Fullerenes; D037742:Nanotubes, Carbon; D015019:Yttrium; D012538:Scandium