Regioselective CF2 functionalization of Sc3N@D3h(5)-C78.

We report the first synthesis and computational study of Sc3N@C78(CF2) - an analog of the previously reported Sc3N@C80(CF2) with a less common carbon cage whose chemical properties presently remain far less studied. Sc3N@C78 appears to be considerably more reactive toward CF2 addition than Sc3N@C80 and somewhat more reactive than C60. Even though the less symmetric D3h(5)-C78 carbon cage offers far broader opportunities for isomerism than Ih-C80, CF2 addition to Sc3N@C78 proceeds regioselectively, similarly to other common fullerene reactions. A DFT survey of the thermodynamic and kinetic aspects of CF2 addition demonstrates that the regioselectivity is controlled kinetically.

Addition of CF2 group to endohedral fullerene Sc3N@Ih-C80.

We report the first successful synthesis of a CF2 derivative of the stable endohedral fullerene Sc3N@Ih-C80. Reaction with CF2ClCOONa yields a single Cs-symmetric Sc3N@C80(CF2) adduct where the CF2 group is inserted into a [6,6]-bond and opens it to 2.3 Å between the bridgehead carbon atoms. As evidenced by absorption and fluorescence spectroscopy as well as cyclic voltammetry, both the HOMO and the LUMO level of Sc3N@C80(CF2) are slightly (ca. 0.1 eV) downshifted with respect to the parent Sc3N@Ih-C80, so the HOMO-LUMO gap remains essentially unchanged. The DFT calculations suggest that the reaction mechanism is not the previously assumed [2 + 1]-cycloaddition of :CF2 carbene but rather nucleophilic addition of CF2Cl- anion followed by elimination of Cl- and closing of the CF2 bridge via intramolecular nucleophilic substitution. Selective formation of the [6,6]-Sc3N@C80(CF2) turns out to be kinetically controlled and promoted by a particular orientation of the endohedral Sc3N cluster with respect to the CF2Cl- addition site. In its turn, the CF2 addend partly hampers the rotation of Sc3N the endohedral cluster compared to its quasi-free reorientations in the parent Sc3N@Ih-C80.

Air-stable redox-active nanomagnets with lanthanide spins radical-bridged by a metal-metal bond.

Engineering intramolecular exchange interactions between magnetic metal atoms is a ubiquitous strategy for designing molecular magnets. For lanthanides, the localized nature of 4f electrons usually results in weak exchange coupling. Mediating magnetic interactions between lanthanide ions via radical bridges is a fruitful strategy towards stronger coupling. In this work we explore the limiting case when the role of a radical bridge is played by a single unpaired electron. We synthesize an array of air-stable Ln2@C80(CH2Ph) dimetallofullerenes (Ln2 = Y2, Gd2, Tb2, Dy2, Ho2, Er2, TbY, TbGd) featuring a covalent lanthanide-lanthanide bond. The lanthanide spins are glued together by very strong exchange interactions between 4f moments and a single electron residing on the metal-metal bonding orbital. Tb2@C80(CH2Ph) shows a gigantic coercivity of 8.2 Tesla at 5 K and a high 100-s blocking temperature of magnetization of 25.2 K. The Ln-Ln bonding orbital in Ln2@C80(CH2Ph) is redox active, enabling electrochemical tuning of the magnetism.

Single molecule magnet with an unpaired electron trapped between two lanthanide ions inside a fullerene.

Increasing the temperature at which molecules behave as single-molecule magnets is a serious challenge in molecular magnetism. One of the ways to address this problem is to create the molecules with strongly coupled lanthanide ions. In this work, endohedral metallofullerenes Y2@C80 and Dy2@C80 are obtained in the form of air-stable benzyl monoadducts. Both feature an unpaired electron trapped between metal ions, thus forming a single-electron metal-metal bond. Giant exchange interactions between lanthanide ions and the unpaired electron result in single-molecule magnetism of Dy2@C80(CH2Ph) with a record-high 100 s blocking temperature of 18 K. All magnetic moments in Dy2@C80(CH2Ph) are parallel and couple ferromagnetically to form a single spin unit of 21 µB with a dysprosium-electron exchange constant of 32 cm-1. The barrier of the magnetization reversal of 613 K is assigned to the state in which the spin of one Dy centre is flipped.

Confining the spin between two metal atoms within the carbon cage: redox-active metal-metal bonds in dimetallofullerenes and their stable cation radicals.

Lanthanide-lanthanide bonds are exceptionally rare, and dimetallofullerenes provide a unique possibility to stabilize and study these unusual bonding patterns. The presence of metal-metal bonds and consequences thereof for the electronic properties of M2@C82 (M = Sc, Er, Lu) are addressed by electrochemistry, electron paramagnetic resonance, SQUID magnetometry and other spectroscopic techniques. A simplified non-chromatographic separation procedure is developed for the isolation of Er2@C82 (Cs(6) and C3v(8) cage isomers) and Sc2@C82 (C3v(8) isomer) from fullerene mixtures. Sulfide clusterfullerenes Er2S@C82 with Cs(6) and C3v(8) fullerene cages are synthesized for the first time. The metal-metal bonding orbital of the spd hybrid character in M2@C82 is shown to be the highest occupied molecular orbital, which undergoes reversible single-electron oxidation with a metal-dependent oxidation potential. Sulfide clusterfullerenes with a fullerene-based HOMO have more positive oxidation potentials. The metal-based oxidation of Sc2@C82-C3v is confirmed by the EPR spectrum of the cation radical [Sc2@C82-C3v]+ generated by chemical oxidation in solution. The spectrum exhibits an exceptionally large a(45Sc) hyperfine coupling constant of 199.2 G, indicating a substantial 4s contribution to the metal-metal bonding orbital. The cationic salt [Er2@C82-C3v]+SbCl6- is prepared, and its magnetization behavior is compared to that of pristine Er2@C82-C3v and Er2S@C82-C3v. The formation of the single-electron Er-Er bond in the cation dramatically changes the coupling between magnetic moments of Er ions.

Synthesis and Isolation of the Titanium-Scandium Endohedral Fullerenes-Sc2 TiC@Ih -C80 , Sc2 TiC@D5h -C80 and Sc2 TiC2 @Ih -C80 : Metal Size Tuning of the Ti(IV) /Ti(III) Redox Potentials.

The formation of endohedral metallofullerenes (EMFs) in an electric arc is reported for the mixed-metal Sc-Ti system utilizing methane as a reactive gas. Comparison of these results with those from the Sc/CH4 and Ti/CH4 systems as well as syntheses without methane revealed a strong mutual influence of all key components on the product distribution. Whereas a methane atmosphere alone suppresses the formation of empty cage fullerenes, the Ti/CH4 system forms mainly empty cage fullerenes. In contrast, the main fullerene products in the Sc/CH4 system are Sc4 C2 @C80 (the most abundant EMF from this synthesis), Sc3 C2 @C80 , isomers of Sc2 C2 @C82 , and the family Sc2 C2 n (2 n=74, 76, 82, 86, 90, etc.), as well as Sc3 CH@C80 . The Sc-Ti/CH4 system produces the mixed-metal Sc2 TiC@C2 n (2 n=68, 78, 80) and Sc2 TiC2 @C2 n (2 n=80) clusterfullerene families. The molecular structures of the new, transition-metal-containing endohedral fullerenes, Sc2 TiC@Ih -C80 , Sc2 TiC@D5h -C80 , and Sc2 TiC2 @Ih -C80 , were characterized by NMR spectroscopy. The structure of Sc2 TiC@Ih -C80 was also determined by single-crystal X-ray diffraction, which demonstrated the presence of a short Ti=C double bond. Both Sc2 TiC- and Sc2 TiC2 -containing clusterfullerenes have Ti-localized LUMOs. Encapsulation of the redox-active Ti ion inside the fullerene cage enables analysis of the cluster-cage strain in the endohedral fullerenes through electrochemical measurements.

Methane as a Selectivity Booster in the Arc-Discharge Synthesis of Endohedral Fullerenes: Selective Synthesis of the Single-Molecule Magnet Dy2TiC@C80 and Its Congener Dy2TiC2@C80.

The use of methane as a reactive gas dramatically increases the selectivity of the arc-discharge synthesis of M-Ti-carbide clusterfullerenes (M=Y, Nd, Gd, Dy, Er, Lu). Optimization of the process parameters allows the synthesis of Dy2TiC@C80-I and its facile isolation in a single chromatographic step. A new type of cluster with an endohedral acetylide unit, M2TiC2@C80, is discovered along with the second isomer of M2TiC@C80. Dy2TiC@C80-(I,II) and Dy2TiC2@C80-I are shown to be single-molecule magnets (SMM), but the presence of the second carbon atom in the cluster Dy2TiC2@C80 leads to substantially poorer SMM properties.

Synthesis and structure of LaSc2N@C(s)(hept)-C80 with one heptagon and thirteen pentagons.

The synthesis and single-crystal X-ray structural characterization of the first endohedral metallofullerene to contain a heptagon in the carbon cage are reported. The carbon framework surrounding the planar LaSc2N unit in LaSc2N@C(s)(hept)-C80 consists of one heptagon, 13 pentagons, and 28 hexagons. This cage is related to the most abundant Ih-C80 isomer by one Stone-Wales-like, heptagon/pentagon to hexagon/hexagon realignment. DFT computations predict that LaSc2N@C(s)(hept)-C80 is more stable than LaSc2N@D5h-C80, and suggests that the low yield of the heptagon-containing endohedral fullerene may be caused by kinetic factors.

[6,6]-Open and [6,6]-closed isomers of C70(CF2): synthesis, electrochemical and quantum chemical investigation.

Novel difluoromethylenated [70]fullerene derivatives, C70(CF2 )n (n=1-3), were obtained by the reaction of C70 with sodium difluorochloroacetate. Two major products, isomeric C70(CF2 ) mono-adducts with [6,6]-open and [6,6]-closed configurations, were isolated and their homofullerene and methanofullerene structures were reliably determined by a variety of methods that included X-ray analysis and high-level spectroscopic techniques. The [6,6]-open isomer of C70(CF2 ) constitutes the first homofullerene example of a non-hetero [70]fullerene derivative in which functionalisation involves the most reactive bond in the polar region of the cage. Voltammetric estimation of the electron affinity of the C70(CF2 ) isomers showed that it is substantially higher for the [6,6]-open isomer (the 70-electron π-conjugated system is retained) than the [6,6]-closed form, the latter being similar to the electron affinity of pristine C70. In situ ESR spectroelectrochemical investigation of the C70(CF2 ) radical anions and DFT calculations of the hyperfine coupling constants provide evidence for the first example of an inter-conversion between the [6,6]-closed and [6,6]-open forms of a cage-modified fullerene driven by an electrochemical one-electron transfer. Thus, [6,6]-closed C70(CF2 ) constitutes an interesting example of a redox-switchable fullerene derivative.