Tuning the interactions between electron spins in fullerene-based triad systems.

A series of six fullerene-linker-fullerene triads have been prepared by the stepwise addition of the fullerene cages to bridging moieties thus allowing the systematic variation of fullerene cage (C60 or C70) and linker (oxalate, acetate or terephthalate) and enabling precise control over the inter-fullerene separation. The fullerene triads exhibit good solubility in common organic solvents, have linear geometries and are diastereomerically pure. Cyclic voltammetric measurements demonstrate the excellent electron accepting capacity of all triads, with up to 6 electrons taken up per molecule in the potential range between -2.3 and 0.2 V (vs Fc(+)/Fc). No significant electronic interactions between fullerene cages are observed in the ground state indicating that the individual properties of each C60 or C70 cage are retained within the triads. The electron-electron interactions in the electrochemically generated dianions of these triads, with one electron per fullerene cage were studied by EPR spectroscopy. The nature of electron-electron coupling observed at 77 K can be described as an equilibrium between doublet and triplet state biradicals which depends on the inter-fullerene spacing. The shorter oxalate-bridged triads exhibit stronger spin-spin coupling with triplet character, while in the longer terephthalate-bridged triads the intramolecular spin-spin coupling is significantly reduced.

Transition metal complexes of a salen-fullerene diad: redox and catalytically active nanostructures for delivery of metals in nanotubes.

A covalently-linked salen-C60 (H2L) assembly binds a range of transition metal cations in close proximity to the fullerene cage to give complexes [M(L)] (M=Mn, Co, Ni, Cu, Zn, Pd), [MCl(L)] (M=Cr, Fe) and [V(O)L]. Attaching salen covalently to the C60 cage only marginally slows down metal binding at the salen functionality compared to metal binding to free salen. Coordination of metal cations to salen-C60 introduces to these fullerene derivatives strong absorption bands across the visible spectrum from 400 to 630 nm, the optical features of which are controlled by the nature of the transition metal. The redox properties of the metal-salen-C60 complexes are determined both by the fullerene and by the nature of the transition metal, enabling the generation of a wide range of fullerene-containing charged species, some of which possess two or more unpaired electrons. The presence of the fullerene cage enhances the affinity of these complexes for carbon nanostructures, such as single-, double- and multiwalled carbon nanotubes and graphitised carbon nanofibres, without detrimental effects on the catalytic activity of the metal centre, as demonstrated in styrene oxidation catalysed by [Cu(L)]. This approach shows promise for applications of salen-C60 complexes in heterogeneous catalysis.

Copper-Catalyzed Formylation of Amines by using Methanol as the C1 Source.

Cu/TEMPO catalyst systems are known for the selective transformation of alcohols to aldehydes, as well as for the simultaneous coupling of alcohols and amines to imines under oxidative conditions. In this study, such a Cu/TEMPO catalyst system is found to catalyze the N-formylation of a variety of amines by initial oxidative activation of methanol as the carbonyl source via formaldehyde and formation of N,O-hemiacetals and oxidation of the latter under very mild conditions. A vast range of amines, including aromatic and aliphatic, primary and secondary, and linear and cyclic amines are formylated under these conditions with good to excellent yields. Moreover, paraformaldehyde can be used instead of methanol for the N-formylation.

Chemical reactions at the graphitic step-edge: changes in product distribution of catalytic reactions as a tool to explore the environment within carbon nanoreactors.

A series of explorative cross-coupling reactions have been developed to investigate the local nanoscale environment around catalytically active Pd(ii)complexes encapsulated within hollow graphitised nanofibers (GNF). Two new fullerene-containing and fullerene-free Pd(ii)Salen catalysts have been synthesised, and their activity and selectivity towards different substrates has been explored in nanoreactors. The catalysts not only show a significant increase in activity and stability upon heterogenisation at the graphitic step-edges inside the GNF channel, but also exhibit a change in selectivity affected by the confinement which alters the distribution of isomeric products of the reaction. Furthermore, the observed selectivity changes reveal unprecedented details regarding the location and orientation of the catalyst molecules inside the GNF nanoreactor, inaccessible by any spectroscopic or microscopic techniques, thus shedding light on the precise reaction environment inside the molecular catalyst-GNF nanoreactor.