Marc Mulet-Gas
Florida State University
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Featured researches published by Marc Mulet-Gas.
Journal of the American Chemical Society | 2012
Paul W. Dunk; Nathan K. Kaiser; Marc Mulet-Gas; Antonio Rodríguez-Fortea; Josep M. Poblet; Hisanori Shinohara; Christopher L. Hendrickson; Alan G. Marshall; Harold W. Kroto
The smallest fullerene to form in condensing carbon vapor has received considerable interest since the discovery of Buckminsterfullerene, C(60). Smaller fullerenes remain a largely unexplored class of all-carbon molecules that are predicted to exhibit fascinating properties due to the large degree of curvature and resulting highly pyramidalized carbon atoms in their structures. However, that curvature also renders the smallest fullerenes highly reactive, making them difficult to detect experimentally. Gas-phase attempts to investigate the smallest fullerene by stabilization through cage encapsulation of a metal have been hindered by the complexity of mass spectra that result from vaporization experiments which include non-fullerene clusters, empty cages, and metallofullerenes. We use high-resolution FT-ICR mass spectrometry to overcome that problem and investigate formation of the smallest fullerene by use of a pulsed laser vaporization cluster source. Here, we report that the C(28) fullerene stabilized by encapsulation with an appropriate metal forms directly from carbon vapor as the smallest fullerene under our conditions. Its stabilization is investigated, and we show that M@C(28) is formed by a bottom-up growth mechanism and is a precursor to larger metallofullerenes. In fact, it appears that the encapsulating metal species may catalyze or nucleate endohedral fullerene formation.
Journal of the American Chemical Society | 2012
Ning Chen; Christine M. Beavers; Marc Mulet-Gas; Antonio Rodríguez-Fortea; Elias J. Munoz; Yu Yang Li; Marilyn M. Olmstead; Alan L. Balch; Josep M. Poblet; Luis Echegoyen
A non isolated pentagon rule metallic sulfide clusterfullerene, Sc(2)S@C(s)(10528)-C(72), has been isolated from a raw mixture of Sc(2)S@C(2n) (n = 35-50) obtained by arc-discharging graphite rods packed with Sc(2)O(3) and graphite powder under an atmosphere of SO(2) and helium. Multistage HPLC methods were utilized to isolate and purify the Sc(2)S@C(72). The purified Sc(2)S@C(s)(10528)-C(72) was characterized by mass spectrometry, UV-vis-NIR absorption spectroscopy, cyclic voltammetry, and single-crystal X-ray diffraction. The crystallographic analysis unambiguously elucidated that the C(72) fullerene cage violates the isolated pentagon rule, and the cage symmetry was assigned to C(s)(10528)-C(72). The electrochemical behavior of Sc(2)S@C(s)(10528)-C(72) shows a major difference from those of Sc(2)S@C(s)(6)-C(82) and Sc(2)S@C(3v)(8)-C(82) as well as the other metallic clusterfullerenes. Computational studies show that the Sc(2)S cluster transfers four electrons to the C(72) cage and C(s)(10528)-C(72) is the most stable cage isomer for both empty C(72)(4-) and Sc(2)S@C(72), among the many possibilities. The structural differences between the reported fullerenes with C(72) cages are discussed, and it is concluded that both the transfer of four electrons to the cage and the geometrical requirements of the encaged Sc(2)S cluster play important roles in the stabilization of the C(s)(10528)-C(72) cage.
Chemical Science | 2013
Ning Chen; Marc Mulet-Gas; Yu Yang Li; Riane E. Stene; Curtis W. Atherton; Antonio Rodríguez-Fortea; Josep M. Poblet; Luis Echegoyen
A new cage isomer of C70, Sc2S@C2(7892)–C70, has been isolated and characterized by mass spectrometry, UV-Vis-NIR absorption spectroscopy, cyclic voltammetry and DFT calculations. The combined experimental and computational studies lead to the unambiguous assignment of the cage symmetry to C2(7892)–C70. The comparison between Sc2S@C2(7892)–C70 and related endohedral structures has been discussed. A close structural resemblance between Sc2S@C2(7892)–C70 and Sc2S@Cs(10528)–C72 suggests that the conversion of these two molecules may be the result of a simple insertion of C2 and the structural difference between Sc2S@C2(7892)–C70 and Sc3N@C2v(7854)–C70 shows that the nature and geometry of the encaged cluster plays an important role on the selection of the non-IPR cage.
Nature Communications | 2014
Paul W. Dunk; Marc Mulet-Gas; Yusuke Nakanishi; Nathan K. Kaiser; Antonio Rodríguez-Fortea; Hisanori Shinohara; Josep M. Poblet; Alan G. Marshall; Harold W. Kroto
An understanding of chemical formation mechanisms is essential to achieve effective yields and targeted products. One of the most challenging endeavors is synthesis of molecular nanocarbon. Endohedral metallofullerenes are of particular interest because of their unique properties that offer promise in a variety of applications. Nevertheless, the mechanism of formation from metal-doped graphite has largely eluded experimental study, because harsh synthetic methods are required to obtain them. Here we report bottom-up formation of mono-metallofullerenes under core synthesis conditions. Charge transfer is a principal factor that guides formation, discovered by study of metallofullerene formation with virtually all available elements of the periodic table. These results could enable production strategies that overcome long-standing problems that hinder current and future applications of metallofullerenes.
Inorganic Chemistry | 2013
Marc Mulet-Gas; Antonio Rodríguez-Fortea; Luis Echegoyen; Josep M. Poblet
Thermal contributions to the free energy have to be taken into account to rationalize the formation of Gd(3)N@C(s)(39663)-C(82), a nitride endohedral metallofullerene that shows a carbon cage with two fused pentagons which is not predicted to have the lowest electronic energy among the isomers of C(82). The lower symmetry and the larger number of pyracylene units of C(s)(39663)-C(82) with respect to the cage in the lowest-energy metallofullerene, C(2v)(39705)-C(82), favor its formation at high temperatures, as seen for other similar cage isomers that encapsulate metal clusters within the C(80) and C(82) families. These cages, which share common motifs with the prototypical I(h)(7)-C(80), are all related by C(2) insertions/extrusions and Stone-Wales transformations.
Chemical Science | 2013
Fang Fang Li; Ning Chen; Marc Mulet-Gas; Vivian Triana; Jesse Murillo; Antonio Rodríguez-Fortea; Josep M. Poblet; Luis Echegoyen
A new titanium-based sulfide clusterfullerene, Ti2S@D3h(24109)-C78, has been successfully synthesized by arc-discharging graphite rods packed with pure TiO2 and graphite powder under an atmosphere of SO2 and helium. Multistage HPLC methods were utilized to isolate and purify the Ti2S@C78, and mass spectrometric characterization confirmed the composition of a Ti2S cluster within a C78 cage. UV-Vis-NIR absorption spectroscopy, electrochemical characterization and extensive DFT calculations led to the assignment of the cage symmetry to D3h(24109)-C78 and suggested an almost linear arrangement of the internal Ti2S cluster, with a formal transfer of six electrons from the cluster to the C78 cage.
Nature Communications | 2017
Marc Mulet-Gas; Laura Abella; Maira R. Cerón; Edison Castro; Alan G. Marshall; Antonio Rodríguez-Fortea; Luis Echegoyen; Josep M. Poblet; Paul W. Dunk
An ultimate goal in carbon nanoscience is to decipher formation mechanisms of highly ordered systems. Here, we disclose chemical processes that result in formation of high-symmetry clusterfullerenes, which attract interest for use in applications that span biomedicine to molecular electronics. The conversion of doped graphite into a C80 cage is shown to occur through bottom-up self-assembly reactions. Unlike conventional forms of fullerene, the iconic Buckminsterfullerene cage, Ih-C60, is entirely avoided in the bottom-up formation mechanism to afford synthesis of group 3-based metallic nitride clusterfullerenes. The effects of structural motifs and cluster–cage interactions on formation of compounds in the solvent-extractable C70–C100 region are determined by in situ studies of defined clusterfullerenes under typical synthetic conditions. This work establishes the molecular origin and mechanism that underlie formation of unique carbon cage materials, which may be used as a benchmark to guide future nanocarbon explorations.An understanding of how caged carbon materials self-assemble from doped graphite is a long-standing challenge. Here, the authors show that distinct bottom-up processes lead to the synthesis of high-symmetry clusterfullerenes.
Inorganic Chemistry | 2016
Laura Abella; Marc Mulet-Gas; Antonio Rodríguez-Fortea; Josep M. Poblet
Different structures have been proposed so far for the C92 isomer that encapsulates M3N (M = La, Ce, Pr). We show here that the electrochemical properties of the predicted most abundant (thermodynamic) isomer for La3N@C92 does not agree with experiment. After a systematic search within the huge number of possible C92 isomers, we propose other candidates with larger electrochemical gaps for La3N@C92 before its structure could be finally determined by X-ray crystallography. We do not discard that the thermodynamic isomer could be detected in future experiments though.
Chemical Science | 2015
Marc Mulet-Gas; Laura Abella; Paul W. Dunk; Antonio Rodríguez-Fortea; Harold W. Kroto; Josep M. Poblet
Comptes Rendus Chimie | 2012
Núria Alegret; Marc Mulet-Gas; Xavier Aparicio-Anglès; Antonio Rodríguez-Fortea; Josep M. Poblet