RESUMO
Additions of adamantylidene (Ad) to M3 N@Ih -C80 (M=Sc, Lu) and Sc3 N@D5h -C80 have been accomplished by photochemical reactions with 2-adamantyl-2,3'-[3H]-diazirine (1). In M3 N@Ih -C80 , the addition led to rupture of the [6,6]- or [5,6]-bonds of the Ih -C80 cage, forming the [6,6]-open fulleroid as the major isomer and the [5,6]-open fulleroid as the minor isomer. In Sc3 N@D5h -C80 , the addition also proceeded regioselectively to yield three major isomeric Ad mono-adducts, despite the fact that there are nine types of C-C bonds in the D5h -C80 cage. The molecular structures of the seven Ad mono-adducts, including the positions of the encaged trimetallic nitride clusters, have been unambiguously determined through single-crystal XRD analyses. Furthermore, results have shown that stepwise addition of Ad to Lu3 N@Ih -C80 affords several Ad bis-adducts, two of which have been isolated and characterized. The X-ray structure of one bis-adduct clearly revealed that the second Ad addition took place at a [6,6]-bond close to an endohedral metal atom. Theoretical calculations have also been performed to rationalize the regioselectivity.
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We compared the chemical reactivity of D2d(23)-C84 and that of Sc2C2@D2d(23)-C84, both having the same carbon cage geometry, in the photolysis of 2-adamantane-2,3'-[3H]-diazirine, to clarify metal-atom doping effects on the chemical reactivity of the carbon cage. Experimental and computational studies have revealed that the chemical reactivity of the D2d(23)-C84 carbon cage is altered drastically by endohedral Sc2C2 doping. The reaction of empty D2d(23)-C84 with the diazirine under photoirradiation yields two adamantylidene (Ad) adducts. NMR spectroscopic studies revealed that the major Ad monoadduct (C84(Ad)-A) has a fulleroid structure and that the minor Ad monoadduct (C84(Ad)-B) has a methanofullerene structure. The latter was also characterized using X-ray crystallography. C84(Ad)-A is stable under photoirradiation, but it interconverted to C84(Ad)-B by heating at 80 °C. In contrast, the reaction of endohedral Sc2C2@D2d(23)-C84 with diazirine under photoirradiation affords four Ad monoadducts (Sc2C2@C84(Ad)-A, Sc2C2@C84(Ad)-B, Sc2C2@C84(Ad)-C, and Sc2C2@C84(Ad)-D). The structure of Sc2C2@C84(Ad)-C was characterized using X-ray crystallography. Thermal interconversion of Sc2C2@C84(Ad)-A and Sc2C2@C84(Ad)-B to Sc2C2@C84(Ad)-C was also observed. The reaction mechanisms of the Ad addition and thermal interconversion were elucidated from theoretical calculations. Calculation results suggest that C84(Ad)-B and Sc2C2@C84(Ad)-C are thermodynamically favorable products. Their different chemical reactivities derive from Sc2C2 doping, which raises the HOMO and LUMO levels of the D2d(23)-C84 carbon cage.
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Bis-silylated and bis-germylated derivatives of Lu3 N@Ih -C80 (3, 4, 5) were successfully synthesized by the photochemical addition of disiliranes 1 a, 1 b or digermirane 2, and fully characterized by spectroscopic, electrochemical, and theoretical studies. Interestingly, digermirane 2 reacts more efficiently than disiliranes 1 a and 1 b because of its good electron-donor properties and lower steric hindrance around the Ge-Ge bond. The 1,4-adduct structures of 3, 4, 5 were unequivocally established by single-crystal X-ray crystallographic analyses. The electrochemical and theoretical studies reveal that the energy gaps between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the 1,4-adducts are remarkably smaller than those of Lu3 N@Ih -C80 , because the electron-donating groups effectively raise the HOMO levels. It is also observed that germyl groups are slightly more electron-donating than the silyl groups on the basis of the redox properties and the HOMO-LUMO energies of 4 and 5. Bis-silylation and bis-germylation are effective and versatile methods for tuning the electronic characteristics of endohedral metallofullerenes.
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The endohedral fullerene once erroneously identified as Sc3@C82 was recently shown to be Sc3C2@Ih-C80, the first example of an open-shell cluster metallofullerene. We herein report that benzyl bromide (1) reacts with Sc3C2@ Ih-C80 via a regioselective radical addition that affords only one isomer of the adduct Sc3C2@Ih-C80(CH2C6H5) (2) in high yield. An X-ray crystallographic study of 2 demonstrated that the benzyl moiety is singly bonded to the fullerene cage, which eliminates the paramagnetism of the endohedral in agreement with the ESR results. Interestingly, X-ray results further reveal that the 3-fold disordered Sc3C2 cluster adopts two different configurations inside the cage. These configurations represent the so-called "planar" form and the computationally predicted, but not crystallographically characterized, "trifoliate" form. It is noteworthy that this is the first crystallographic observation of the "trifoliate" form for the Sc3C2 cluster. In contrast, crystallographic investigation of a Sc3C2@Ih-C80/Ni(OEP) cocrystal, in which the endohedral persists in an open-shell structure with paramagnetism, indicates that only the former form occurs in pristine Sc3C2@ Ih-C80. These results demonstrate that the cluster configuration in EMFs is highly sensitive to the electronic structure, which is tunable by exohedral modification. In addition, the electrochemical behavior of Sc3C2@Ih-C80 has been markedly changed by the radical addition, but the absorption spectra of the pristine and the derivative are both featureless. These results suggest that the unpaired electron of Sc3C2@Ih-C80 is buried in the Sc3C2 cluster and does not affect the electronic configuration of the cage.
Assuntos
Compostos de Benzil/química , Fulerenos/química , Compostos Organometálicos/síntese química , Escândio/química , Cristalografia por Raios X , Modelos Moleculares , Estrutura Molecular , Compostos Organometálicos/química , Espectrometria de Massas por Ionização e Dessorção a Laser Assistida por MatrizRESUMO
[11]Cycloparaphenylene ([11]CPP) selectively encapsulates La@C82 to form the shortest possible metallofullerene-carbon nanotube (CNT) peapod, La@C82 â[11]CPP, in solution and in the solid state. Complexation in solution was affected by the polarity of the solvent and was 16â times stronger in the polar solvent nitrobenzene than in the nonpolar solvent 1,2-dichlorobenzene. Electrochemical analysis revealed that the redox potentials of La@C82 were negatively shifted upon complexation from free La@C82 . Furthermore, the shifts in the redox potentials increased with polarity of the solvent. These results are consistent with formation of a polar complex, (La@C82 )(δ-) â[11]CPP(δ+) , by partial electron transfer from [11]CPP to La@C82 . This is the first observation of such an electronic interaction between a fullerene pea and CPP pod. Theoretical calculations also supported partial charge transfer (0.07) from [11]CPP to La@C82 . The structure of the complex was unambiguously determined by X-ray crystallographic analysis, which showed the La atom inside the C82 near the periphery of the [11]CPP. The dipole moment of La@C82 was projected toward the CPP pea, nearly perpendicular to the CPP axis. The position of the La atom and the direction of the dipole moment in La@C82 â[11]CPP were significantly different from those observed in La@C82 âCNT, thus indicating a difference in orientation of the fullerene peas between fullerene-CPP and fullerene-CNT peapods. These results highlight the importance of pea-pea interactions in determining the orientation of the metallofullerene in metallofullerene-CNT peapods.
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The reaction mechanism of the Diels-Alder reaction of paramagneticendohedral metallofullerene, La@C82, and 1,2,3,4,5-pentamethylcyclopentadiene was studied theoretically and experimentally. Theoretical calculations revealed that this reaction proceeds via a concerted mechanism that includes formation of a stable intermediate. The activation energy of a retro-Diels-Alder reaction was also studied experimentally, which is in good agreement with theoretical results.
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The dynamic positions of the dimetallic cluster inside the mid-sized spherical cages of C(80)-C(82) have been seldom studied, despite the high abundance of M(2)@C(2n) (2n = 80, 82) species among various endohedral metallofullerenes. Herein, using crystallographic methods, we first unambiguously map the metal positions for both Ce(2)@D(5h)-C(80) and Ce(2)@I(h)-C(80), showing how the symmetry or geometrical change in cage structure can influence the motional behavior of the cluster. Inside the D(5h) cage, the primary cerium sites have been identified along a cage belt of the contiguous hexagons, which suggests the significant influence of such a cage motif on endohedral cluster motion. Further analysis revealed a distorted D(5h) cage owing to the "punch-out" effect of cerium atoms. The consequence is the presence of two localized electrostatic potential minima inside the cage of (D(5h)-C(80))(6-), thus reflecting the primary ionic cerium-cage interaction. In contrast, a different motional behavior of Ce(2) cluster was observed inside the I(h) cage. With the major cerium sites, the molecule of Ce(2)@I(h)-C(80) presented an approximate D(2h) configuration. With the combined theoretical study, we propose that the additional unidentified influence of Ni(II) (OEP) (OEP = octaethylporphyrin) might be also relevant for the location of cerium sites inside the I(h) cage.
Assuntos
Cério/química , Fulerenos/química , Teoria Quântica , Cristalografia por Raios X , Modelos MolecularesRESUMO
Although all the pure-carbon fullerene isomers above C60 reported to date comply with the isolated pentagon rule (IPR), non-IPR structures, which are expected to have different properties from those of IPR species, are obtainable either by exohedral modification or by endohedral atom doping. This report describes the isolation and characterization of a new endohedral metallofullerene (EMF), La2@C76, which has a non-IPR fullerene cage. The X-ray crystallographic result for the La2@C76/[Ni(II)(OEP)] (OEP=octaethylporphyrin) cocrystal unambiguously elucidated the C(s)(17,490)-C76 cage structure, which contains two adjacent pentagon pairs. Surprisingly, multiple metal sites were distinguished from the X-ray data, which implies dynamic behavior for the two La(3+) cations inside the cage. This dynamic behavior was also corroborated by variable-temperature (139)La NMR spectroscopy. This phenomenon conflicts with the widely accepted idea that the metal cations in non-IPR EMFs invariably coordinate strongly with the negatively charged fused-pentagon carbons, thereby providing new insights into modern coordination chemistry. Furthermore, our electrochemical and computational studies reveal that La2@C(s)(17,490)-C76 has a larger HOMO-LUMO gap than other dilanthanum-EMFs with IPR cage structures, such as La2@D(3h)(5)-C78 and La2@I(h)(7)-C80, which implies that IPR is no longer a strict rule for EMFs.
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We describe, for the first time, the application of magnetic circular dichroism (MCD) spectroscopy and time-dependent density functional theory (TD-DFT) calculations using B3LYP and M06-2X functionals to characterize the electronic transitions of endohedral metallofullerenes (EMFs). Results revealed that the electronic transitions of La@C(2v)-C(82), La(2)@I(h)-C(80), and Sc(3)N@I(h)-C(80) can be assigned using these techniques. Particularly, a difference in the electronic transitions between La(2)@I(h)-C(80) and Sc(3)N@I(h)-C(80), which is invisible in absorption spectra, was observed clearly in MCD spectra. The observed MCD bands agree well with the oscillator strengths calculated using the B3LYP functional. In addition, the MCD bands of La(2)@I(h)-C(80) were altered upon [5,6]-addition, demonstrating that the MCD spectroscopy is sensitive to chemical functionalization of EMFs, and that it is therefore powerful to distinguish [5,6]-adducts from pristine La(2)@I(h)-C(80), although no marked difference exists in their absorption spectra.
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It has been an interesting finding that reactions of M@C(2v)(9)-C(82) (M = Y, La, Ce, Gd) with diazirine adamantylidene (AdN(2), 1) gave rise to only two monoadduct isomers, indicating that the cage reactivity of monometallofullerenes is not dependent on the type of the internal metal. However, we found here that Sc@C(2v)(9)-C(82) shows an exceptional chemical reactivity toward the electrophile 1, affording four monoadduct isomers (2a-d). Single-crystal X-ray diffraction crystallographic results of the most abundant isomer (2a) confirm that the addition takes place at a [6,6]-bond junction which is very close to the internal metal ion. Theoretical calculations reveal that 2 out of the 24 nonequivalent cage carbons of Sc@C(2v)(9)-C(82) are highly reactive toward 1, but only one cage carbon of the other M@C(2v)-C(82) (M = Y, La, Ce, Gd) is sufficiently reactive. The exceptional chemical property of Sc@C(2v)(9)-C(82) is associated with the small ionic radius of Sc(3+), which allows stronger metal-cage interactions and makes back-donation of charge from the cage to the metal more pronounced. Our results have provided new insights into the art of altering the chemical properties of fullerene molecules at the atomic level, which would be useful in the future in utilizing EMFs in quantum computing systems.
Assuntos
Adamantano/química , Sondas Moleculares , Cristalografia por Raios X , Modelos MolecularesRESUMO
Single crystals of three soluble Yb@C(82) isomers, namely, Yb@C(2)(5)-C(82), Yb@C(s)(6)-C(82), and Yb@C(2v)(9)-C(82), cocrystallized with Ni(II)(octaethylporphyrin), allowed accurate crystallographic elucidation of their molecular structures in terms of both cage symmetry and metal location. Multiple metal positions were found in all these isomers, but the major metal sites were found in some specific regions within these cages. Specifically, the Yb(2+) ion prefers to reside close to a hexagonal ring in Yb@C(2)(5)-C(82) and Yb@C(2v)(9)-C(82) but a [5,6,6]-junction carbon atom in Yb@C(s)(6)-C(82). Theoretical calculations at the B3LYP level revealed that these metal positions all correspond to energy minima from the electrostatic potential maps and give rise to the most stable configurations of these Yb@C(82) isomers. Furthermore, it is noteworthy that this is the first report on X-ray crystallographic studies of such metallofullerenes with the popular C(2v)(9)-C(82) encapsulating a divalent metal ion, described as M(2+)@[C(2v)(9)-C(82)](2-).
Assuntos
Fulerenos/química , Metaloporfirinas/química , Ítrio/química , Cristalografia por Raios X , Modelos MolecularesRESUMO
An endohedral metallofullerene, La(2)@C(80), is covalently linked to the strong electron acceptor 11,11,12,12-tetracyano-9,10-anthra-p-quinodimethane (TCAQ) by means of the Prato reaction, affording two different [5,6]-metallofulleropyrrolidines, namely 1a and 2a. 1a and 2a were isolated and fully characterized by means of MALDI-TOF mass, UV-vis-NIR absorption, and NMR spectroscopies. In addition, cyclic voltammetry (CV) and differential pulse voltammetry (DPV) corroborated the unique redox character of 2a, that is, the presence of the electron-donating La(2)@C(80) and the electron-accepting TCAQ. Although a weak electronic coupling dictates the interactions between La(2)@C(80) and TCAQ in the ground state, time-resolved transient absorption experiments reveal that in the excited state (i.e., π-π* centered at La(2)@C(80)) the unprecedented formation of the (La(2)@C(80))(â¢+)-(TCAQ)(â¢-) radical ion pair state evolves in nonpolar and polar media with a quantum efficiency of 33%.
Assuntos
Antraquinonas/química , Elétrons , Fulerenos/química , Lantânio/química , Modelos Moleculares , Estrutura MolecularRESUMO
Little is known about the chemical properties of carbide cluster metallofullerenes (CCMFs). Here we report the photochemical reaction of a newly assigned CCMF Sc(2)C(2)@C(2v)(5)-C(80) with 2-adamantane-2,3-[3H]-diazirine (AdN(2), 1), which provides a carbene reagent under irradiation. Five monoadduct isomers (2a-2e), with respective abundances of 20%, 40%, 25%, 5%, and 10%, were isolated and characterized with a combination of experimental techniques including unambiguous single-crystal X-ray crystallography. Results show that the two Sc atoms of the bent Sc(2)C(2) cluster tend to move in most cases, whereas the C(2)-unit is almost fixed. Accordingly, it is difficult to explain the addition patterns by considering the strain and charge density on the cage with a fixed cluster, and thus a moving cluster may account for the addition patterns. These results show that the situation of CCMFs is more complicated than those in other metallofullerenes. Furthermore, a thermal isomerization process from 2b to 2c was observed, confirming that the most abundant isomer 2b is a kinetically favored adduct. Finally, it is revealed that the electronic and electrochemical properties of pristine Sc(2)C(2)@C(2v)(5)-C(80) have been markedly altered by exohedral modification.
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The reaction of tetrazine 1 with Sc(3)C(2)@C(80) exclusively affords the open-cage derivative 2 instead of the expected C(2)-inserted derivative 3 bearing a four-membered ring, as previously obtained for C(60). The structure of 2 has been firmly established by NMR spectroscopy and theoretical calculations. EPR spectroscopy shows that a single Sc atom of the Sc(3)C(2) cluster gets located within the bulge created by the bridging addend, which is a first step toward release of the internal metal atoms.
Assuntos
Carbono/química , Escândio/química , Modelos Moleculares , Estrutura Molecular , Tetrazóis/químicaRESUMO
Functionalization of endohedral metallofullerenes has been shown to differ depending on photochemical or thermal pathways. We report that Lu(3)N@I(h)-C(80) reacts with thermally generated bis(2,6-diethylphenyl)silylene with high selectivity and forms monosilylated derivative 1b. Unexpectedly, 1b undergoes photochemical conversion to afford isomer 1a under ambient light. These adducts were characterized using NMR, visible-near-IR spectroscopy, and matrix-assisted laser desorption ionization time-of-flight mass spectrometry. Single-crystal X-ray structure determination of 1a reveals a rare example of an open 1,2-adduct at the [5,6]-ring junction of the I(h)-C(80) cage. The electrochemical study reveals that the redox potentials of 1a and 1b are shifted cathodically compared to those of pristine Lu(3)N@I(h)-C(80) and that monosilylation is effective to fine-tune the electronic properties of endohedral metallofullerenes as well as empty fullerenes. Density functional theory calculations were also performed, which provide a theoretical basis for the structures and the behavior of the encapsulated Lu(3)N cluster.
Assuntos
Fulerenos/química , Cromatografia Líquida de Alta Pressão , Cristalografia por Raios X , Espectroscopia de Ressonância Magnética , Espectrometria de Massas , Modelos Moleculares , Espectroscopia de Luz Próxima ao InfravermelhoRESUMO
Electron donor-acceptor conjugates of paramagnetic endohedral metallofullerenes and π-extended tetrathiafulvalene (exTTF) were synthesized, characterized, and probed with respect to intramolecular electron transfer involving paramagnetic fullerenes. UV-vis-NIR absorption spectroscopy complemented by electrochemical measurements attested to weak electronic interactions between the electron donor, exTTF, and the electron acceptor, La@C(82), in the ground state. In the excited state, photoexcitation powers a fast intramolecular electron transfer to yield an ion and radical ion pair state consisting of one-electron-reduced La@C(82) and of one-electron-oxidized exTTF.
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X-ray analyses of the cocrystals of a series of carbide cluster metallofullerenes Sc(2)C(2)@C(2n) (n = 40-42) with cobalt(II) octaethylporphyrin present new insights into the molecular structures and cluster-cage interactions of these less-explored species. Along with the unambiguous identification of the cage structures for the three isomers of Sc(2)C(2)@C(2v)(5)-C(80), Sc(2)C(2)@C(3v)(8)-C(82), and Sc(2)C(2)@D(2d)(23)-C(84), a clear correlation between the cluster strain and cage size is observed in this series: Sc-Sc distances and dihedral angles of the bent cluster increase along with cage expansion, indicating that the bending strain within the cluster makes it pursue a planar structure to the greatest degree possible. However, the C-C distances within Sc(2)C(2) remain unchanged when the cage expands, perhaps because of the unusual bent structure of the cluster, preventing contact between the cage and the C(2) unit. Moreover, analyses revealed that larger cages provide more space for the cluster to rotate. The preferential formation of cluster endohedral metallofullerenes for scandium might be associated with its small ionic radius and the strong coordination ability as well.
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Metal positions in endohedral metallofullerenes (EMFs) are of special importance because their molecular symmetry and intrinsic properties are strongly influenced by the location and motion of the encapsulated metals. X-ray analyses of the cocrystals of Gd@C(2v)(9)-C(82) with nickel(II) octaethylporphyrin [Ni(II)(OEP)] reveal that the Gd(3+) cation is off-center, being located under a hexagonal ring along the 2-fold axis of the C(2v)(9)-C(82) cage. This result is in sharp contrast to that of a previous study, showing that Gd@C(2v)(9)-C(82) has an anomalous endohedral structure, with the metal being positioned over a [6,6] bond, which is opposite to the hexagonal ring along the C(2) axis (Phys. Rev. B 2004, 69, 113412). In agreement with theoretical calculations and related studies, it is conclusive that the single rare-earth metal in M@C(2v)(9)-C(82) always tends to coordinate with the hexagonal ring along the 2-fold axis, instead of interacting with the [6,6] bond on the other end, regardless of the type of metal atom.
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Single crystal X-ray diffraction studies of Yb@C(2v)(3)-C(80)·Ni(II)(OEP)·CS(2)·1.5C(6)H(6) (OEP = octaethylporphinate) reveal that a relatively flat region of the fullerene interacts with the Ni(II)(OEP) molecule, featuring shape-matching interactions. Surprisingly, it is found that the internal metal is located under a hexagonal carbon ring apart from the 2-fold axis of the C(2v)(3)-C(80) cage, presenting the first example of metallofullerenes with an asymmetrically positioned metal. Such an anomalous location of Yb(2+) is associated with its strong ability to pursue a large coordination number and the lack of hexagon along the C(2) axis of C(2v)(3)-C(80). It is accordingly assumed that a suitable cage hexagon is most likely to be preferred by the single rare earth metal to stay behind inside a medium-sized fullerene, such as C(80) and C(82).
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Unambiguous X-ray crystallographic results of the carbene adduct of Sc(2)C(82) reveal a new carbide cluster metallofullerene with the unexpected C(2v)(5)-C(80) cage, that is, Sc(2)C(2)@C(2v)(5)-C(80). More interestingly, DFT calculations and NMR results disclose that the dynamic motion of the internal Sc(2)C(2) cluster depends strongly on temperature. At 293 K, the cluster is fixed inside the cage with two nonequivalent Sc atoms on the mirror plane, thereby leading to C(s) symmetry of the whole molecule. However, when the temperature increases to 413 K, the (13)C and (45)Sc NMR spectra show that the cluster rotates rapidly inside the C(2v)(5)-C(80) cage, featuring two equivalent Sc atoms and weaker metal-cage interactions.