ИСТИНА

The design and manipulation of molecular components which possess the necessary information to self assemble into well defined architectures represents a major route towards designing functional materials with molecular precision. This idea can be utilised to bridge the gap between top down and bottom up engineering, creating ordered materials on the macroscale from molecular building blocks leading to materials with improved performance. C60 fullerene is a spherical nanosized building block ideal for incorporation into supramolecular architectures forming ordered 3D (crystals and liquid crystals), 2D (surface layers) and 1D (chains inside carbon nanotubes) structures. Fullerenes and their derivatives possess redox and optical properties that make them ideal components in systems for photoactivation, such as photovoltaics and photocatalysis. As transition metal complexes also provide a wealth of redox, optical and magnetic properties, the combination of fullerene with coordinated transition metal ions can thus be utilised to form molecular or supramolecular systems with tuneable physiochemical properties. The synthesis of fullerene derivatives containing metal binding groups has received significant attention, however, the rapid advancement of this area has been hindered by difficulties in the synthesis of functionalised fullerene ligands or the poor solubility of the resultant metal complexes. Therefore, no ‘universal’ {fullerene}-{metal binding group} combination has been identified that can coordinate a wide variety of metal centres. We present the synthesis of a new metal receptor-C60 diad assembly incorporating the tetradentate N2O2-coordinating Schiff-base ligand salen. We demonstrate that the salen moiety in this system can bind to a wide range of transition metals cations (VIV, CrIII, MnII, FeIII, CoII, NiII, CuII, ZnII and PdII) to form stable and soluble metal complexes. The introduction of redox-active metal centres enables fine-tuning of the electron-acceptor properties of the salen-C60 compounds and significantly broadens the range of available reduced states, which are both important for the application of fullerenes in photovoltaics and electrocatalysis. Furthermore, many of the reduced species possess two or more unpaired electrons presenting an opportunity for the exploitation of the electrochemically-controlled magnetic states of salen-C60 complexes in quantum information processing and molecular spintronic devices. These complexes have also demonstrated catalytic activity in (ep)oxidation reactions, characteristic of metal-salen complexes. In addition, the presence of a fullerene cage bound to a transition metal containing moiety exploits the affinity of fullerene molecules for all forms of sp2-hybridised carbon and facilitates the deposition of these metal centres into a variety of carbon-based nanostructures. This provides a new methodology for the delivery and organisation of redox and magnetically active species in linear arrangements inside carbon nanotubes and represents an important step towards the development of molecular electronic devices for data storage, molecular switches, sensors, photoconductors and photoactive diads and new generation of heterogeneous catalysts.