Journal ArticleDOI
Methanofullerene Molecular Scaffolding: Towards C60-substituted poly(triacetylenes) and expanded radialenes, preparation of a C60–C70 hybrid derivative, and a novel macrocyclization reaction
Jean-Franjois Nierengarten,Andreas Herrmann,Rik R. Tykwinski,Markus Riittimann,François Diederich,Corinne Boudon,Jean-Paul Gisselbrecht,Maurice Gross +7 more
TLDR
In this paper, the synthesis of expanded radialenes and expanded C60-C70 fullerene derivatives is described, which are precursors to C60substituted poly(triacetylenes) (PTAs, Fig. 1) and expanded radialene (Fig. 2) is described.Abstract:
The synthesis of (E)-hex-3-ene-l, 5-diynes and 3-methylidenepenta-1, 4-diynes with pendant methano[60]-fullerene moieties as precursors to C60-substituted poly(triacetylenes) (PTAs, Fig. 1) and expanded radialenes (Fig. 2) is described. The Bingel reaction of diethyl (E)-2, 3-dialkynylbut-2-ene-1, 4-diyl bis(2-bromopropane-dioates) 5 and 6 with two C60 molecules (Scheme 2) afforded the monomeric, silyl-protected PTA precursors 9 and 10 which, however, could not be effectively desilylated (Scheme 4). Also formed during the synthesis of 9 and 10, as well as during the reaction of C60 with thedesilylated analogue 16 (Scheme5), were the macrocyclic products 11, 12, and 17, respectively, resulting from double Bingel addition to one C-sphere. Rigorous analysis revealed that this novel macrocyclization reaction proceeds with complete regio- and diastereoselectivity. The second approach to a suitable PTA monomer attempted N, N′-dicyclohexylcarbodiimide(DCC)-mediated esterification of (E)-2, 3-diethynylbut-2-ene-l, 4-diol (18, Scheme 6) with mono-esterified methanofullerene-dicarboxylic acid 23; however, this synthesis yielded only the corresponding decarboxylated methanofullerene-carboxylic ester 27 (Scheme 7). To prevent decarboxylation, a spacer was inserted between the reacting carboxylic-acid moiety and the methane C-atom in carboxymethyl ethyl 1, 2-methano[60]fullerene-61, 61-dicarboxylate (28, Scheme 8), and DCC-mediated esterification with diol 18 afforded PTA monomer 32 in good yield. The formation of a suitable monomeric precursor 38 to C60-substituted expanded radialenes was achieved in 5 steps starting from dihydroxyacetone (Schemes 9 and 10), with the final step consisting of the DCC-mediated esterification of 28 with 2-[1-ethynyl(prop-2-ynylidene)]propane-1, 3-diol (33). The first mixed C60-C70 fullerene derivative 49, consisting of two methano[60]fullerenes attached to a methano[70]fullerene, was also prepared and fully characterized (Scheme 13). The Cs-symmetrical hybrid compound was obtained by DCC-mediated esterification of bis[2-(2-hydroxy-ethoxy)ethyl] 1, 2-methano[70]fullerene-71, 71-dicarboxylate (46) with an excess of the C60-carboxylic acid 28. The presence of two different fullerenes in the same molecule was reflected by its UV/VIS spectrum, which displayed the characteristic absorption bands of both the C70 and C60 mono-adducts, but at the same time indicated no electronic interaction between the different fullerene moieties. Cyclic voltammetry showed two reversible reduction steps for 49, and comparison with the corresponding C70 and C60 mono-adducts 46 and 30 indicated that the three fullerenes in the composite fullerene compound behave as independent redox centers.read more
Citations
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Structural aspects of fullerene chemistry--a journey through fullerene chirality.
Carlo Thilgen,François Diederich +1 more
Journal ArticleDOI
Conjugated oligoenynes based on the diethynylethene unit.
Journal ArticleDOI
Synthesis and properties of molecular rods. 2. Zig-zag rods
Journal ArticleDOI
Macrocyclization on the fullerene core: Direct regio‐ and diastereoselective multi‐functionalization of [60]fullerene, and synthesis of fullerene‐dendrimer derivatives
Jean-François Nierengarten,Tilo Habicher,Roland Kessinger,Francesca Cardullo,François Diederich,Volker Gramlich,Jean-Paul Gisselbrecht,Corinne Boudon,Maurice Gross +8 more
TL;DR: In this article, a bis-functionalization method for the double Bingel reaction with optically active bis-malonate derivatives was proposed, which allowed the diastereoselective preparation of optically-active fullerene derivatives and, ultimately, the enanti-lective extraction of higher cyclopropanated adducts.
Journal ArticleDOI
A new pyridyl-substituted methanofullerene derivative. Photophysics, electrochemistry and self-assembly with zinc(II) meso-tetraphenylporphyrin (ZnTPP)
Nicola Armaroli,François Diederich,Luis Echegoyen,Tilo Habicher,Lucia Flamigni,Giancarlo Marconi,Jean-François Nierengarten +6 more
TL;DR: In this paper, a new methanofullerene derivative with a pyridine residue at the methano bridge (PC60) has been synthesized, and its electrochemical and photophysical properties were investigated in toluene solution along with those of the analogous fullerene mono-malonate adduct RC60, which does not contain the pyridyl moiety.
References
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Journal ArticleDOI
Solid C60: a new form of carbon
TL;DR: In this article, a new form of pure, solid carbon has been synthesized consisting of a somewhat disordered hexagonal close packing of soccer-ball-shaped C60 molecules.
Book
Handbook of conducting polymers
TL;DR: In this paper, the authors presented the theory and properties of conjugated polymers, including transport, optical, and self-assembly properties of poly(3,4-Ethylenedioxythiophene)-polymers.
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Efficient light-emitting diodes based on polymers with high electron affinities
TL;DR: In this article, a new family of processible poly(cyanoterephthalylidene)s was used for electron injection and hole injection in poly(p-phenylene vinylene) (PPV) diodes.
Journal ArticleDOI
Preparation and Characterization of Fulleroid and Methanofullerene Derivatives
TL;DR: In this paper, the synthesis and complete characterization of soluble derivatives of C-60 for applications to physics and biology was described, where the goal of the strategy was to have a "modular" approach in order to be able to easily vary a functional group attached indirectly to the cluster.
Journal ArticleDOI
Organic molecular soft ferromagnetism in a fullerene c60.
Pierre-Marc Allemand,K. C. Khemani,A. Koch,Fred Wudl,Karoly Holczer,Steven Donovan,George Grüner,Joe D. Thompson +7 more
TL;DR: The properties of an organic molecular ferromagnet with a Curie temperature of 16.1 kelvin are described, where the ferromagnetic state shows no remanence, and the temperature dependence of the magnetization below ;Tc does not follow the behavior expected of a conventional ferromaagnet.