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Title: Endohedral fullerenes: Synthesis, isolation, mono- and bis -functionalization

Abstract

Here, in this paper, we present a short overview of the contribution of our research group to the discovery, functionalization and characterization of unprecedented endohedral fullerenes. We also report a comprehensive study of regioselective bis-1,3-dipolar cycloadditions to cluster endohedral fullerenes M 3N@I h-C 80 (M = Lu, Y and Er) and the spectroscopic characterization of the new bis-adducts obtained.

Authors:
 [1];  [2];  [3];  [4]
  1. University of Texas at El Paso, El Paso, TX (United States). Department of Chemistry; Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Physical and Life Sciences
  2. University of Texas at El Paso, El Paso, TX (United States); Istituto Italiano di Tecnologia (Italy). Nano Carbon Materials Laboratory; University of Genova (Italy). Department of Chemistry and Industrial Chemistry
  3. Indiana-Purdue University at Fort Wayne, Fort Wayne, IN (United States). Department of Chemistry
  4. University of Texas at El Paso, El Paso, TX (United States). Department of Chemistry
Publication Date:
Research Org.:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1409946
Report Number(s):
LLNL-JRNL-720246
Journal ID: ISSN 0020-1693
Grant/Contract Number:
AC52-07NA27344
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Inorganica Chimica Acta
Additional Journal Information:
Journal Volume: 468; Journal Issue: C; Journal ID: ISSN 0020-1693
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY

Citation Formats

Cerón, Maira R., Maffeis, Viviana, Stevenson, Steven, and Echegoyen, Luis. Endohedral fullerenes: Synthesis, isolation, mono- and bis -functionalization. United States: N. p., 2017. Web. doi:10.1016/j.ica.2017.03.040.
Cerón, Maira R., Maffeis, Viviana, Stevenson, Steven, & Echegoyen, Luis. Endohedral fullerenes: Synthesis, isolation, mono- and bis -functionalization. United States. doi:10.1016/j.ica.2017.03.040.
Cerón, Maira R., Maffeis, Viviana, Stevenson, Steven, and Echegoyen, Luis. Wed . "Endohedral fullerenes: Synthesis, isolation, mono- and bis -functionalization". United States. doi:10.1016/j.ica.2017.03.040. https://www.osti.gov/servlets/purl/1409946.
@article{osti_1409946,
title = {Endohedral fullerenes: Synthesis, isolation, mono- and bis -functionalization},
author = {Cerón, Maira R. and Maffeis, Viviana and Stevenson, Steven and Echegoyen, Luis},
abstractNote = {Here, in this paper, we present a short overview of the contribution of our research group to the discovery, functionalization and characterization of unprecedented endohedral fullerenes. We also report a comprehensive study of regioselective bis-1,3-dipolar cycloadditions to cluster endohedral fullerenes M3N@Ih-C80 (M = Lu, Y and Er) and the spectroscopic characterization of the new bis-adducts obtained.},
doi = {10.1016/j.ica.2017.03.040},
journal = {Inorganica Chimica Acta},
number = C,
volume = 468,
place = {United States},
year = {Wed Mar 29 00:00:00 EDT 2017},
month = {Wed Mar 29 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
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  • In this paper, we discuss the results of our study of the synthesis of endohedral iron-fullerenes. A low energy Fe{sup +} ion beam was irradiated to C{sub 60} thin film by using a deceleration system. Fe{sup +}-irradiated C{sub 60} thin film was analyzed by high performance liquid chromatography and laser desorption/ ionization time-of-flight mass spectrometry. We investigated the performance of the deceleration system for using a Fe{sup +} beam with low energy. In addition, we attempted to isolate the synthesized material from a Fe{sup +}-irradiated C{sub 60} thin film by high performance liquid chromatography.
  • The reaction of Y[sub 3](OR)[sub 7]Cl[sub 2](THF)[sub 2] (R = CMe[sub 3]) with alkali metal cyclopentadienyl reagents, MC[sub 5]R[sub 5] (M = Na or K), in toluene disrupts the trimetallic structure of the starting material and forms the halide-free bimetallic compounds [(C[sub 5]R[sub 5])Y([mu]-OR) (OR)][sub 2] (C[sub 5]R[sub 5] = C[sub 5]Me[sub 5], 1; C[sub 5]H[sub 5], 2; C[sub 5]H[sub 4]Me, 3; C[sub 5]H[sub 4]SiMe[sub 3], 4). 1 and 4 were also obtained from the reaction of YCl[sub 3](THF)[sub x] with 2 equiv of NaOCMe[sub 3] and 1 equiv of MC[sub 5]R[sub 5] in toluene at reflux. Also prepared inmore » this manner was the indenyl analog, [(C[sub 9]H[sub 7])Y([mu]-OR)(OR)][sub 2], 5. X-ray crystallographic data on 1, 2, 4, and 5 reveal that structurally analogous complexes are formed in these reactions despite the different substituents on the cyclopentadienyl rings. In each of these four complexes, the two cyclopentadienyl ligands are arranged in a cis orientation around a (RO)Y([mu]-OR)[sub 2]Y(OR) central core which has similar metrical parameters in each compound. The ligand redistribution product (C[sub 5]H[sub 5])[sub 2]Y([mu]-OR)[sub 2]Y(C[sub 5]H[sub 5])(OR), 6, is also isolated as a minor component in the reaction between Y[sub 3](OR)[sub 7]Cl[sub 2](THF)[sub 2] and NaC[sub 5]H[sub 5]. 2-5 react with LiCH[sub 2]SiMe[sub 3] to unexpectedly lose LiC[sub 5]R[sub 5] instead of LiOR. 65 refs., 9 figs., 3 tabs.« less
  • A series of Cr/sup III/(PP)/sub x/X/sub 6-2n/ complexes have been prepared and characterized in which n = 1 or 2, PP = 2,2'-bipyridine or 1,10-phenanthroline, and X = NH/sub 3/, en/2, acac/sup /minus///2, CN/sup /minus//, or NCS/sup /minus//. The (/sup 2/E)Cr/sup III/(PP)/sub n/X/sub 6-2n/ excited states are much weaker oxidants than their (/sup 2/E)Cr(PP)/sub 3//sup 2+/ parents. The visible spectroscopy of the Cr/sup III/(PP)/sub n/X/sub 6-2n/ complexes is complicated by overlapping absorptions. A very prominent feature of these absorptions is a regular, relatively narrow band progression with energies independent of X. This progression is attributed to direct excitation into themore » triplet-/pi/* ligand manifold states, with the forbidden singlet-triplet transitions of the free polypyridyl ligand(s) being relaxed by spin-spin coupling in the Cr(III) complexes. The (/sup 2/E)Cr(III) lifetimes, /tau/(/sup 2/E), of these complexes in fluid and glass solutions are strongly temperature dependent but approach a limiting value at low temperatures: (/tau/(/sup 2/E))/sup /minus/1/ = k/sub r/ + k/sub nr//sup 0/ + A exp(/minus/E/sub a//RT), where k/sub r/ and k/sub nr//sup 0/ are the nearly temperature-independent radiative and nonradiative relaxation rate constants, respectively. The room-temperature lifetimes of the mixed-ligand complexes vary over a 30-fold range, and /tau/(/sup 2/E) is much smaller for these complexes than found for their Cr(phen)/sub 3//sup 3+/ and Cr(bpy)/sub 3//sup 3+/ parents. The range of lifetimes is not strongly temperature dependent since E/sub a/ = 33 /plus minus/ 2 kJ mol/sup /minus/1/ and A = (3.5 /plus minus/ 1.1) /times/ 10/sup 11/ s/sup /minus/1/ for the Cr/sup III/(PP)/sub n/X/sub 6-2n/ complexes (X ne CN/sup /minus//); for X = CN/sup /minus//, A /approx/ 7 /times/ 10/sup 12/ s/sup /minus/1/. 65 references, 8 figures, 9 tables.« less