New Vistas in Fullerene Chemistry: Organosulfur Compounds Expand the Performance Of Carbon Nanomaterials

Abstract

Introducing organosulfur moieties into EMFs is a successful approach for the elucidation of electron transfer behavior of EMFs because the introduced sulfur atoms promote active redox properties in the fullerene molecules. Complexation of La@C₈₂ and unsaturated thiacrown ether, for instance, shows remarkable host–guest interaction and electron transfer to the fullerene. In contrast to these intermolecular electron-accepting properties of EMFs, intramolecular properties were revealed through studies of covalently bonded La₂@C₈₀ or La@C₈₂ and π-extended tetrathiafulvalene (exTTF) dyads. These first milestones on the electron transfer behavior have inspired us to ascertain and then expand our knowledge of the unique characteristics of EMFs. These findings suggest potential applications of EMFs based on their unique molecular structure and electronic and magnetic properties as novel carbon nanomaterials.

GRAPHICAL ABSTRACT

Keywords:

• Endohedral metallofullerenes
• π-extended tetrathiafulvalene
• intramolecular electron transfer
• intermolecular electron transfer
• donor–acceptor dyads
• porphyrins

Acknowledgments

This work was supported in part by a Grant-in-Aid for Scientific Research on Innovative Areas (20108001, “π-Space”), Grants-in-Aid for Scientific Research (A) (20245006) and (B) (24350019), The Next Generation Super Computing Project (Nanoscience Project), the Nanotechnology Support Project, Grants-in-Aid for Scientific Research on Priority Areas (20036008 and 20038007), and a Specially Promoted Research grant from the Ministry of Education, Culture, Sports, Science, and Technology of Japan and by the Strategic Japanese−Spanish Cooperative Program funded by JST and MINECO (Projects PLE-2009-0039 and PIB2010JP-00196).