Phosphorylated methano[60]fullerenes containing nitroxyl radicals: synthesis, structures, and electrochemical behavior

Gubskaya, V. P.; Berezhnaya, L. Sh.; Yanilkin, V. V.; Морозов, В. И.; Nastapova, N. V.; Efremov, Yu. Ya.; Нуретдинов, И. А.

doi:10.1007/s11172-006-0017-5

Cited by 10 publications

(8 citation statements)

References 29 publications

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“…10,11 There have been several studies into the synthesis and study of nitroxide fullerene derivatives, mainly fulleropyrrolidines, 12-14 but it is interesting to note that there has been practically no work into the synthesis of nitroxide methanofullerenes. 15 Methanofullerenes are, from the point of view of synthesis, one of the most developed classes of organic fullerene derivatives. [16][17][18] The fullerene core in methanofullerenes usually contains 1-4 nitroxide groups, but can contain more.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, structure and biological activity of nitroxide malonate methanofullerenes

et al. 2007

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study has also revealed some flaws in the previous model of inter-double-helix hydrogen bonding. [1] Imberty, A.; Chanzy, H.; Pérez, S.; Buléon, A.; Tran, V. Functionally substituted fullerene derivatives are of interest since it is possible to obtain both biologically active substances and new materials for nanotechnology on their basis. The spherical platform of fullerene allows one to design molecules with various fragments, which are responsible for the specific properties. At the same time the crystal structure of such compounds is studied insufficiently, that is why Crystallographic Data Bases contain information about not more than 80 fullerene C60 derivatives structures. Interesting feature of these compounds (both derivatives and fullerene complexes) in solid state is their active participation in pi-electronic interactions between each other and with other compounds incorporating aromatic fragments. Owing to these interactions the compounds can form in a crystal the supramolecular structures of various type, that, apparently, finds reflection in their particular properties. Basing on literature structural data for organic derivative of fullerene and on our original X-ray data for the bis-and mono-adducts of the methanofullerenes and pyrrolidino-fullerenes, we have analysed the intermolecular interactions, crystal packing and supramolecular structure of these compounds from the point of view of such interactions. It was found, that in spite of the presence of large substituents in the molecules and solvate molecules in the crystals, which hinder such interactions, the fullerene fragments are closely packed with different fullerene environments-honeycomb structure, zigzag-chain,  dimers, columns and layers, and preferably interact face-to-face with the 5-and 6-membered aromatic rings. The majority of the compounds forms 2D-structures-layers of various topology with fullerenes coordination equal to 3 or 4. Presence of molecules-guests with aromatic fragments or aromatic fragments in the fullerene derivatives leads to their obligatory participation in such interactions and to the destruction of the fullerene-fullerene interactions. Recently we carried out the synthesis of malonate nitroxide metanofullerene, which shows, in combination with known anticancer drug cyclophosphamide, the high antitumor activity against leukemia P-388. It was shown by X-ray single crystal analysis that methanofullerene with two nitroxide groups has a diamond-like environment in the crystal due to fullerene-fullerene interactions [1]. In the same time the first examples of the phosphorylated mono-and bis-methano-fullerenes with large substituents have lower coordination of fragments-zigzag chains and pi-dimers. The comparative analysis of the results for the organic derivatives and for the fullerene C60 inclusion compounds is presented. The topology of the crystals is analysed additionally on the base of proposed model of localization of hydrophilic and hydrophobic regions in the crystals of organic compounds. Keywords: hydrogen...

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Section: Introductionmentioning

confidence: 99%

Synthesis, structure and biological activity of nitroxide malonate methanofullerenes

et al. 2007

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“…The synthesis and properties of Ia and IIa were described previously [7]. The synthetic procedure for the preparation of Ib and IIb is based on the BingelHirsch reaction [8] and is achieved by direct treatment of the fullerene C60 with corresponding malonate precursors in the presence of CBr 4 and DBU.…”

Section: Methodsmentioning

confidence: 99%

“…7). For Qt, in the strong coupling limit, the dipolar interaction is /)Qi = (1/6)(DT + DReT + DR2T) -4--(1/12)DRtR2 (7) and, using the tensors already mentioned (DRIT, DR2T, DT) , we obtained the following ZFS parameters: DQi = 3.7 mT and EQi = 0.6 mT. The latter values are in better agreement with those used for the simulation.…”

Section: Biradicalsmentioning

confidence: 99%

TR-EPR of single and double spin-labeled C60 derivatives in frozen matrices

et al. 2006

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Abstraet. Time-resolved electron paramagnetic resonance spectra of two single spin-labeled and two double spin-labeled C6o derivatives in frozen solution are recorded with pulsed laser excitation and 100 ns time resolution. Quartet and quintet excited species are detected which arise from the electron spin coupling of the triplet excited fullerene moiety with the unpaired spin(s) of the nitroxide label(s). Despite the similar molecular structure, in both series of single and double labeled derivatives a different behavior was found, which is due to substantial difference of the energy of exchange coupling.

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“…19 In order to improve the stability of such hybrid catalysts, we studied other TEMPO derivatives with phosphonic acid function. This anchoring function, wellknown to ensure better stability in the aqueous medium than the carboxylate function, 20 has been recently employed for the immobilization of nitroxyl radicals on various supports such as fullerene for electrochemical reduction reaction 21 or iron oxide (Fe 3 O 4 ) for the oxidation of secondary benzylic and aliphatic alcohol. 22 We report herein the synthesis of new phosphonic-based hybrid catalysts (Figure 1) for selective oxidation of sugar.…”

Section: Introductionmentioning

confidence: 99%

Nitroxide-Grafted Nanometric Metal Oxides for the Catalytic Oxidation of Sugar

Omri

Bécuwe

Courty

et al. 2019

ACS Appl. Nano Mater.

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A new series of ([2,2,6,6-tetramethylpiperidin-1-yl]oxy) (TEMPO) catalysts supported on nanometric metal oxides (TiO2, AlO2, CeO2) and their efficiency for sugar oxidation are herein described. The preparation of such hybrid catalysts was carried out by modification of a metal oxide surface with a monolayer of phosphonic linker bearing a TEMPO radical. All prepared catalysts were carefully characterized by diffuse reflectance Fourier-transform infrared spectroscopy, thermogravimetric analysis, X-ray diffraction, and transmission electron microscopy. The efficiency of these new hybrid TEMPO supported materials for sugar oxidation was evaluated on methyl α-d-glucoside, as a model carbohydrate. The three hybrid catalysts showed high selectivity, activity, and stability, suggesting a promising potential for rapidly obtaining acid sugar derivatives.

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Phosphorylated methano[60]fullerenes containing nitroxyl radicals: synthesis, structures, and electrochemical behavior

Cited by 10 publications

References 29 publications

Synthesis, structure and biological activity of nitroxide malonate methanofullerenes

Synthesis, structure and biological activity of nitroxide malonate methanofullerenes

TR-EPR of single and double spin-labeled C60 derivatives in frozen matrices

Nitroxide-Grafted Nanometric Metal Oxides for the Catalytic Oxidation of Sugar

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