Self-assembly of fullerenes

Hahn U, Cardinal F, Nierengarten J-F. Supramolecular chemistry for the self-assembly of fullerene-rich dendrimers. New J Chem 2007 31 1128-1138. 

SELF-ASSEMBLY OF FULLERENE MOLECULES FROM ENSEMBLES OF RANDOMLY ORIENTED C2 MOLECULES... 

Figure 31 Self-assembling of fullerene and porphyrin on gold nanoparticles. (Reproduced from Ref. 37. Royal Society of...

Although fullerenes have frequently been used as a building block in the preparation of supramolecular systems, recently a few examples have been reported in which hydrogen-bonding motifs dictate the ensemble arrangement. In one of the first examples, the formation of a self-assembled monolayer (SAM), was carried out by self-assembly of fullerenes, endowed with a monobenzo 18-crown-6 ether moiety on a gold surface (vide infra) ... 

Diederich, R, Echegoyen, L., Gomez-Lopez, M., Kessinger, R. and Stoddart, J. R The self-assembly of fullerene-containing [2]pseudorotaxanes Formation of a supramolecular C q dimer. J. Chem. Soc., Perkin Trans. 2, 1577-1586, 1999. 

Mechanism of the Self-Assembly of Fullerenes, The spontaneous formation of fullerenes under the extreme high energetic conditions imposed by the carbon vapor plasma implies a considerable entropy loss which should be considered in... 

Smalley R E 1992 Self-assembly of the fullerenes Accounts.Chem. Res. 25 98-105... 

Hawker C J, Seville P M and White J W 1994 The synthesis and characterization of a self-assembling amphiphilic fullerene J. Org. Chem. 59 3503-5... 

Akiyama T, Imahori H, Ajawakom A and Sakata Y 1996 Synthesis and self assembly of porphyrin-linked fullerene on gold surface using S-Au linkage Chem. Lett. 907-8... 

The first ever reported molecule to undergo encapsulation was fullerene, which spontaneously and accidentally ended up in the tubes during post-processing of raw tubes prepared via the pulsed laser vaporization method. This could be considered a milestone in the self-assembling of a new class of nanomaterials [78]. 

Nierengarten et al. have reported many examples of fullerene-rich dendrimers, obtained by either covalent linking or self-assembly of proper units.72,73 A very interesting example is represented by a family of fullerodendrimers from the first to the third generation, containing a hexaphenylbenzene core and 6, 12, and 24 C60 units (compound 26 in Fig. 6.19) at the periphery, respectively.74... 

The results given indicate the electrochemical method for the synthesis of nanostructured carbon materials to be promising. In the reaction space, dissipative self-assembly of carbon compounds takes place by the action of electric discharges. In this case, structures of new type can be formed, which are transitional between polycyclic aromatic hydrocarbons and fullerenes, nanotubes. 

FIGURE 2.2 Supramolecular nanostructures for light driven energy and electron transfer. This research is focused on rational design and study of self-assembled porphyrin, fullerene, and carbon nanotube bearing supramolecular complexes and nanostructures. 

The self-assembly of molecules containing two AADD faces into supramole-cular polymers has been observed by employing molecules containing two ureidopyrimidone moieties such as 45 [27], and the same logic has been used to construct tapes in which fullerenes [205] and siloxanes [206] are present as part of the backbone. 

Smalley, R.E. (1992) Self-assembly of the fullerenes. Accounts of Chemical Research, 25, 98-105. 

Another example of self-assembly of porphyrin-containing polymer was illustrated by Li et al.73 Polyacetylene functionalized with fullerene and zinc porphyrin pendant groups were synthesized by polymerizing the corresponding fullerene/porphyrin substituted alkyne monomers with rhodium(I) norbomadiene catalyst (Scheme 5.5).74 Polymers with different ratio of C60 and porphyrin were synthesized. The polymers showed photocurrent response when the thin films were irradiated with white light, which was due to the electron transfer from the photo-excited porphyrin to the C60 units. In addition, the copolymers aggregated into ellipse-shaped nanorod structures with a diameter of approximately 100 nm and a length of... 

FIGURE 5.12 Schematic representation of the self-assembly of Zn-metallated multiporphyrin dendrimer containing 24 donors with 12 fullerene-appended bipyridine ligands for enhanced charge separation. 

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