Endohedral metallofullerenes in self-assembled monolayers.

A method has been developed for the attachment of a dithiolane group to endohedral metallofullerenes via a 1,3-dipolar cycloaddition reaction. This sulfur-containing functional group serves as an anchor, enabling efficient immobilisation of endohedral fullerenes on Au(111) surfaces at room temperature, directly from the solution phase. The functionalised fullerenes form disordered monolayers that exhibit no long-range ordering, which is attributed to both the strong bonding of the dithiolane anchor to the surface and to the conformational flexibility of the functional group. Endohedral fullerenes Er(3)N@C(80) and Sc(3)N@C(80) have been used as models for functionalisation and subsequent surface deposition. Their chemical reactivity towards dithiolane functionalisation and their surface behaviour have been compared to that of C(60). The endohedral fullerenes appear to be significantly less reactive towards the functionalisation than C(60), however they bind in a similar manner to a gold surface as their dithiolane terminated C(60) counterparts. The optical activity of Er(3)N@C(80) molecules is preserved after attachment of the functional group. We report a splitting of the endohedral Er(3+) emission lines due to the reduction in symmetry of the functionalised fullerene cage, as compared to the highly symmetrical icosahedral C(80) cage of pristine Er(3)N@C(80).

Variable-force tapping atomic force microscopy as a tool in the characterization of organic devices.

A common method for characterizing the phase separation of materials in mixtures is tapping mode atomic force microscopy (AFM). However, AFM results are influenced by surface-energy effects and the employed tapping force, and it might therefore be difficult to attain correct information regarding the bulk with such a surface-imaging technique. In this work, we present a way of imaging material phase separation in an improved manner by recording a series of AFM images at different tapping force. More specifically, we have employed the variable-force AFM method on organic mixtures, comprising a conjugated polymer (MEH-PPV) and an ion-conducting polymer electrolyte (PEO-XCF(3)SO(3), X=Li, K, Rb), and we demonstrate that it is capable of reversibly sampling such materials not only on the surface, but also (indirectly) in the topmost part of the bulk. The analysis of the evolution of AFM phase images allows us to (indirectly) gain information about the bulk-phase separation of materials. We find that the variable-force AFM results correlate well with the device performance of light-emitting electrochemical cells employing such organic mixtures as the active material.