© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Mater. 2010, 22, 4220–4248 4220 www.advmat.de www.MaterialsViews.com PROGRESS REPORT wileyonlinelibrary.com By Francesco Giacalone* and Nazario Martín* New Concepts and Applications in the Macromolecular Chemistry of Fullerenes [∗] Dr. F. Giacalone Department of Organic Chemistry “E. Paternò” Università di Palermo Viale delle Scienze s/n, Ed. 17, 90128 Palermo (Italy) Fax: +39-091-566825 E-mail: fgiacalone@unipa.it Prof. N. Martín Departamento de Química Orgánica I Facultad de Ciencias Químicas Universidad Complutense de Madrid Ciudad Universitaria s/n, 28040 Madrid, Spain IMDEA- Nanociencia Campus de la Universidad Autónoma de Madrid 28049 Madrid (Spain) E-mail: nazmar@quim.ucm.es DOI: 10.1002/adma.201000083 1. Introduction Fullerene-containing polymers is a very active field that inte- grates two expanding scientific areas, i.e., those of fullerenes and polymers. However, whereas polymers have shown their applicability for social needs in a huge number of examples, fullerenes despite their outstanding mechanical, [1] chemical, [2] electrochemical [3] and photophysical [4] properties still are not widely employed in real applications. In this regard, the combination of the unique fullerenes with the highly versatile and easily processable polymers merges into a new field in which novel materials exhibiting the properties of fullerenes can be handled with the advan- tages of processability of polymers. Although a variety of previous review papers partially covered the many exam- ples of polymers that make use of fuller- enes, only recently we have carried out a comprehensive revision of this field and organized the rich existing bibliography from a chemical viewpoint, with special emphasis on the synthesis and properties exhibited by the different materials. [5,6] The aim of the present paper is to update the previous work by bringing together the most significant advances that have occurred in the field of fullerene polymers during the last few years involving different macromolecular structures combined with fullerenes. Furthermore, we have added some recent hybrid systems involving fuller- enes and carbon nanotubes (CNTs). In fact, CNTs can be used as polydisperse materials with variable length and diameters, and are able to allocate C 60 molecules inside their cavity forming nanopeapods which can undergo a further and amazing poly- merization reaction to generate double-walled CNTs. On the other hand, in addition to new issues such as water-soluble C 60 -polymers, biodegradable C 60 -polymers or polyfullerene-based membranes, new fullerene-containing hybrids such as fullerene-silica hybrid materials or DNA-C 60 hybrids are also discussed. Donor-acceptor (D-A) fullerene poly- mers maintain the interest of the scientific community due to their implications for photovoltaic applications and, thus, the most recent advances have also been discussed in the text. The last part is dedicated to the increasing field of supramo- lecular polymers involving fullerenes, which opens a new avenue for facilitating the integration of fullerenes into poly- mers and other supramolecular organizations such as the inter- esting self-assembling polyfullerene-based systems. Finally, we would like to remark that this review is mainly focused on the singular features and applications of the different classes of fullerene-containing polymers and, consequently, they have been organized in a systematic and unprecedented way according to the different properties they exhibit. A new classification on the different types of fullerene-containing polymers is presented according to their different properties and applications they exhibit in a variety of fields. Because of their interest and novelty, water-soluble and biodegradable C 60 -polymers are discussed first, followed by polyfullerene- based membranes where unprecedented supramolecular structures are presented. Next are compounds that involve hybrid materials formed from fullerenes and other components such as silica, DNA, and carbon nanotubes (CNTs) where the most recent advances have been achieved. A most relevant topic is still that of C 60 -based donor-acceptor (D–A) polymers. Since their application in photovoltaics D–A polymers are among the most realistic appli- cations of fullerenes in the so-called molecular electronics. The most relevant aspects in these covalently connected fullerene/polymer hybrids as well as new concepts to improve energy conversion efficiencies are presented. The last topics disccused relate to supramolecular aspects that are in involved in C 60 -polymer systems and in the self-assembly of C 60 -macromolecular structures, which open a new scenario for organizing, by means of non-covalent interactions, new supramolecular structures at the nano- and micrometric scale, in which the combination of the hydrofobicity of fullerenes with the versatility of the noncovalent chemistry afford new and spectacular superstructures.