271785-57-0Relevant articles and documents
Hierarchically ordered self-assembly of amphiphilic bifullerenes
Wasserthal, Lennard,Schade, Boris,Ludwig, Kai,Boettcher, Christoph,Hirsch, Andreas
, p. 5961 - 5966 (2014)
A series of novel functionalised dumbbell-shaped bifullerenes in which two [5.0] pentakis-adducts of C60 are covalently connected by cyclic bismalonates were synthesised. These dimeric compounds, carrying various combinations of hydrophilic and hydrophobic addends, self-assemble in aqueous solution towards supramolecular architectures of different structural complexity as observed by cryogenic transmission electron microscopy (cryo-TEM). The detailed analysis of the image data revealed an unprecedented hierarchical aggregation behaviour. Whereas completely hydrophilic substituted bifullerenes formed profoundly monodisperse populations of small oligomeric elementary micelles consisting of only three or four bifullerene molecules in a supposedly bent conformation, their amphiphilic equivalents underwent a hierarchical two-step assembly process towards larger spherical and even rod-like structures. The data suggest that the hierarchical assembly process is driven by hydrophobic interactions of preformed tetrameric elementary micelles. Nanoscopic dumbbell exercises: Studying the assembly behaviour of novel synthesised amphiphilic bifullerene derivatives in aqueous solution by cryogenic transmission electron microscopy reveals an unprecedented hierarchical self-assembly towards spherical and rod-like aggregates (see graphic).
Synthesis and study of trannulene derivatives of fullerenes
Khakina,Peregudov,Troyanov,Troshin
, p. 264 - 279 (2012)
A series of trannulenes C60F15[CX(COOR) 2]3 (X = COOMe, Br; R = Me, Et, Prn, n-Hex, But, (CH2)3NHCOOBut) was synthesized. The first water-soluble trannulenes containing six carboxyl groups (C60F15[C(COOMe)(COOH)2]3) or six protonated amino groups (C60F15[C(COOMe)(COO(CH 2)3NH3 +CF3COO -)2]3) were obtained. The compositions and structures of all compounds were proved by mass spectrometry, 1H, 13C, and 19F NMR spectroscopy, and other physicochemical methods. The reactivity of trannulenes was studied for the first time. The unique isomerization of trannulenes to triumphenes accompanied by the migration of three organic addends from one hemisphere of the fullerene cage to another hemisphere was discovered. The structures of the isomerization products were proved using single-crystal X-ray diffraction analysis and 1H, 13C, and 19F NMR spectroscopy. The concerted cascade of isomerization, elimination, and addition reactions was accomplished, which made it possible to obtain photoactive dyads C60F14R 2=A (R = C(X)(COOR)2, A is a fragment of fullerenes C 60 or C70, anthracene, or pentacene). These dyads contain the electron-deficient fluorofullerene core and electron-donor (with respect to the fluorofullerene core of the molecule) addend A. Photoinduced charge separation can occur in these systems, which makes them analogs of natural photosynthetic antennas.
Synthesis and characterization of water-soluble amino fullerene derivatives
Richardson, Christine F.,Schuster, David I.,Wilson, Stephen R.
, p. 1011 - 1014 (2000)
A series of amino-substituted methanofullerene derivatives were prepared by mono-, tris-, and hexa-Bingel-Hirsch reactions using an N-protected malonate derivative. Upon scission of the protecting groups, the e,e,e-tris- and octahedral Th hexa-methano amino fullerenes were found to be among the most water-soluble fullerene derivatives yet prepared. 3He NMR data on corresponding adducts of 3He@C60 helped verify the assigned structures. UV spectral studies confirmed the influence of aggregation on solubility of these adducts in water.
Synthesis and spectroscopic characterization of the first symmetrically and nonsymmetrically substituted fluorinated emerald-green trannulenes C 60F15R3 soluble in polar media and water
Troshin, Pavel A.,Khakina, Ekaterina A.,Zhilenkov, Alexander V.,Peregudov, Alexander S.,Troshina, Olesya A.,Kozlovskii, Viacheslav I.,Polyakova, Natalya V.,Lyubovskaya, Rimma N.
scheme or table, p. 1037 - 1045 (2010/04/29)
The first water-soluble C3V-symmetrical trannulene derivatives of fluorofullerene C60F18 possessing six carboxylic or ammonium ion groups have been synthesized and spectrally characterized. The stability of emerald-green aqueous solutions of these compounds was investigated. A novel, synthetic route was developed for a step-by-step derivatization of C60F18 with different organic C-H acids that: yielded nonsymmetrically substituted C60F15R 2R trannulenes. The synthesized trannulenes were loaded with polar carboxylic groups that improved greatly the solubility of these compounds in aqueous media, We showed that four solubilizing COOH groups could be introduced onto the fullerene cage of C60F15R2R' trannulenes with R substituent and then some additional organic functionality could be attached independently with R', The R' substituent might potentially comprise a ligand responsible for selective targeting of the whole trannulene molecule to some specific tissues or intracellular structures. The demonstrated loading of the fluorofullerene core with polar carboxylic or ammonium groups might be considered as an important step towards the design of sophisticated water-soluble trannulene-based assembles for biomedical applications.
