PERGAMON Carbon 38 (2000) 1587–1598 Synthesis and electronic properties of donor-linked fullerenes towards photochemical molecular devices a, a a * Jean-Franc ¸ois Nierengarten , Jean-Franc ¸ois Eckert , Delphine Felder , a b b b Jean-Franc ¸ois Nicoud , Nicola Armaroli , Giancarlo Marconi , Veronica Vicinelli , c c c Corinne Boudon , Jean-Paul Gisselbrecht , Maurice Gross , d d d e Georges Hadziioannou , Victor Krasnikov , Lahoussine Ouali , Luis Echegoyen , e Sheng-Gao Liu a ´ ´ ´ Institut de Physique et Chimie des Materiaux de Strasbourg, Groupe des Materiaux Organiques, Universite Louis Pasteur and CNRS, 23 rue du Loess, 67037 Strasbourg, France b Istituto di Fotochimica e Radiazioni d’ Alta Energia del CNR, via Gobetti 101, 40129 Bologna, Italy c ´ Laboratoire d’ Electrochimie et de Chimie Physique du Corps Solide, Universite Louis Pasteur and CNRS,4 rue Blaise Pascal, 67008 Strasbourg, France d Department of Polymer Chemistry and Materials Science Centre, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands e Department of Chemistry, University of Miami, Coral Gables, FL 33214, USA Abstract We report our recent progress in the synthesis and the study of donor-linked fullerenes. The synthesis of C polyadducts 60 with well defined three-dimensional structure provides versatile building blocks for the preparation of porphyrin–fullerene derivatives with unusual stereochemical and electronic properties. Phenanthroline ligands substituted with fullerene- functionalized dendritic wedges and their copper(I) complexes have been prepared. Electrochemical and photophysical investigations have shown that the bis(phenanthroline)copper(I) central core is somehow buried in a dendritic black box. Finally, fullerene–oligophenylenevinylene hybrids have been synthesised in order to provide a molecular approach to photovoltaic conversion, and to prevent the morphology problems resulting from the phase separation in donor–acceptor composites.  2000 Elsevier Science Ltd. All rights reserved. Keywords: A. Fullerene; C. Spectrophotometry; D. Electronic properties, Electrochemical properties, Optical properties 1. Introduction [5–44]. It should be pointed out that the C group appears 60 to be a particularly interesting electron acceptor in photo- In light of their unusual physical and chemical prop- chemical molecular devices because of its symmetrical erties, fullerenes and their derivatives appear to be attrac- shape, its large size and the properties of its p-electron tive candidates for the construction of supramolecular system. The characteristics of C are in stark contrast with 60 assemblies and advanced materials [1–3]. The recent those of common acceptors with smaller size such as progress in the chemistry of C [4] allows the preparation benzoquinone. Actually, accelerated charge separation and 60 of many fullerene derivatives covalently bound to donor decelerated charge recombination has been observed in a moieties [5,6]. These systems provide entry into intra- fullerene-based acceptor–donor system when compared to molecular processes such as energy and electron transfer the equivalent benzoquinone-based system [26]. This has been interpreted simply by the smaller reorganization energy ( l) of C compared with those of small acceptors: 60 *Corresponding author. Tel.: 133-3-8810-7163; fax: 133-3- the smaller reorganization energy of C positions the 8810-7246. 60 photoinduced charge separation rate upward along the E-mail address: niereng@michelangelo.u-strasbg.fr (J.-F. Nierengarten). normal region of the Marcus parabolic curve, while forcing 0008-6223 / 00 / $ – see front matter  2000 Elsevier Science Ltd. All rights reserved. PII: S0008-6223(99)00290-0