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Title: Photoelectron Spectroscopy and Electronic Structures of Fullerene Oxides: C 60O x - ( x = 1-3)

Abstract

We report a photoelectron spectroscopy (PES) study on a series of fullerene oxides, C 60O x - (x = 1-3). The PES spectra reveal one isomer for C 60O -, two isomers for C 60O 2 -, and multiple isomers for C 60O 3 -. Compared to C 60, the electronic structures of C 60O x are only slightly perturbed, resulting in similar anion photoelectron spectra. The electron affinity of C 60O x was observed to increase only marginally with the number of oxygen atoms, x, from 2.683 eV for C 60, to 2.745 eV for C 60O, and 2.785 eV/2.820 eV for C 60O 2 (two isomers). We also carried out theoretical calculations, which confirmed the observed isomers and showed that all the fullerene oxides are in the form of epoxide. Finally, the PES and theoretical calculations, as well as molecular orbital analysis, indicate that addition of oxygen atoms to the C 60 cage only modifies the local carbon network and leave the rest of the fullerene cage largely intact geometrically and electronically.

Authors:
; ; ;
Publication Date:
Research Org.:
Environmental Molecular Sciences Laboratory (EMSL), Richland, WA (United States); Washington State Univ., Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER)
OSTI Identifier:
1152412
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory; Journal Volume: 109; Journal Issue: 49
Country of Publication:
United States
Language:
English

Citation Formats

Wang, Xue-Bin, Woo, Hin-Koon, Kiran, Boggavarapu, and Wang, Lai-Sheng. Photoelectron Spectroscopy and Electronic Structures of Fullerene Oxides: C60O x- (x = 1-3). United States: N. p., 2005. Web. doi:10.1021/jp055775e.
Wang, Xue-Bin, Woo, Hin-Koon, Kiran, Boggavarapu, & Wang, Lai-Sheng. Photoelectron Spectroscopy and Electronic Structures of Fullerene Oxides: C60O x- (x = 1-3). United States. doi:10.1021/jp055775e.
Wang, Xue-Bin, Woo, Hin-Koon, Kiran, Boggavarapu, and Wang, Lai-Sheng. Thu . "Photoelectron Spectroscopy and Electronic Structures of Fullerene Oxides: C60O x- (x = 1-3)". United States. doi:10.1021/jp055775e.
@article{osti_1152412,
title = {Photoelectron Spectroscopy and Electronic Structures of Fullerene Oxides: C60O x- (x = 1-3)},
author = {Wang, Xue-Bin and Woo, Hin-Koon and Kiran, Boggavarapu and Wang, Lai-Sheng},
abstractNote = {We report a photoelectron spectroscopy (PES) study on a series of fullerene oxides, C60Ox- (x = 1-3). The PES spectra reveal one isomer for C60O-, two isomers for C60O2-, and multiple isomers for C60O3-. Compared to C60, the electronic structures of C60Ox are only slightly perturbed, resulting in similar anion photoelectron spectra. The electron affinity of C60Ox was observed to increase only marginally with the number of oxygen atoms, x, from 2.683 eV for C60, to 2.745 eV for C60O, and 2.785 eV/2.820 eV for C60O2 (two isomers). We also carried out theoretical calculations, which confirmed the observed isomers and showed that all the fullerene oxides are in the form of epoxide. Finally, the PES and theoretical calculations, as well as molecular orbital analysis, indicate that addition of oxygen atoms to the C60 cage only modifies the local carbon network and leave the rest of the fullerene cage largely intact geometrically and electronically.},
doi = {10.1021/jp055775e},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 49,
volume = 109,
place = {United States},
year = {Thu Dec 01 00:00:00 EST 2005},
month = {Thu Dec 01 00:00:00 EST 2005}
}
  • We report a photoelectron spectroscopy (PES) study on a series of fullerene oxides, C600x- (x = 1-3). The PES spectra reveal one isomer for C600x-, two isomers for C6002-, and multiple isomers for C6003-. Compared to C60, the electronic structures of C600x are only slightly perturbed, resulting in similar anion photoelectron spectra. The electron affinity of C600x was observed to increase only marginally with the number of oxygen atoms, x, from 2.683 eV for C60, to 2.745 eV for C600, and 2.785 eV/2.820 eV for C6002 (two isomers). We also carried out theoretical calculations, which confirmed the observed isomers andmore » showed that all the fullerene oxides are in the form of epoxide. The PES and theoretical calculations, as well as molecular orbital analysis, indicate that addition of oxygen atoms to the C60 cage only modifies the local carbon network and leave the rest of the fullerene cage largely intact geometrically and electronically.« less
  • A photoelectron spectroscopy investigation of the fluorofullerene anions C 60F n - (n = 17, 33, 35, 43, 45, 47) and the doubly-charged anions C 60F 34 2- and C 60F 46 2- is reported. The electron affinities for the corresponding neutral molecules, C 60F n, were directly measured and were found to increase as n increased, reaching the extremely high value of 5.66 ± 0.10 eV for C 60F 47. Density functional calculations suggest that the experimentally observed species C 60F 17 -, C 60F 35 -, and C 60F 47 - were each formed by reductive-defluorination of themore » parent fluorofullerene, C 3v-C 60F 18, C 60F 36 (a mixture of isomers), and D 3-C 60F 48, respectively, without rearrangement of the remaining fluorine atoms. The DFT-predicted stability of C 60F 47 - was verified by its generation by chemical reduction from D 3-C 60F 48 in chloroform solution at 25 °C and its characterization by mass spectrometry and 19F NMR spectroscopy. Further reductive-defluorination of C 60F 47 - in solution resulted in the selective generation of a new fluorofullerene, D 2-C 60F 44, which was also characterized by mass spectrometry and 19F NMR spectroscopy.« less
  • The reaction of Re{sub 2}O{sub 7} with XeF{sub 6} in anhydrous HF provides a convenient route to high-purity ReO{sub 2}F{sub 3}. The fluoride acceptor and Lewis base properties of ReO{sub 2}F{sub 3} have been investigated leading to the formation of [M][ReO{sub 2}F{sub 4}] [M = Li, Na, Cs, N(CH{sub 3}){sub 4}], [K][Re{sub 2}O{sub 4}F{sub 7}], [K][Re{sub 2}O{sub 4}F{sub 7}]{center_dot}2ReO{sub 2}F{sub 3}, [Cs][Re{sub 3}O{sub 6}F{sub 10}], and ReO{sub 2}F{sub 3}(CH{sub 3}CN). The ReO{sub 2}F{sub 4}{sup {minus}}, Re{sub 2}O{sub 4}F{sub 7}{sup {minus}}, and Re{sub 3}O{sub 6}F{sub 10{sup {minus}} anions and the ReO{sub 2}F{sub 3}(CH{sub 3}CN) adduct have been characterized in the solidmore » state by Raman spectroscopy, and the structures [Li][ReO{sub 2}F{sub 4}], [K][Re{sub 2}O{sub 4}F{sub 7}], [K][Re{sub 2}O{sub 4}F{sub 7}]{center_dot}2ReO{sub 2}F{approximately}3}, [Cs][Re{sub 3}O{sub 6}F{sub 10}], and ReO{sub 3}F(CH{sub 3}CN){sub 2}{center_dot}CH{sub 3}CN have been determined by X-ray crystallography. The structure of ReO{sub 2}F{sub 4}{sup {minus}} consists of a cis-dioxo arrangement of Re-O double bonds in which the Re-F bonds trans to the oxygen atoms are significantly lengthened as a result of the trans influence of the oxygens. The Re{sub 2}O{sub 4}F{sub 7}{sup {minus}} and Re{sub 3}O{sub 6}F{sub 10}{sup {minus}} anions and polymeric ReO{sub 2}F{sub 3} are open chains containing fluorine-bridged ReO{sub 2}F{sub 4} units in which each pair of Re-O bonds are cis to each other and the fluorine bridges are trans to oxygens. The trans influence of the oxygens is manifested by elongated terminal Re-F bonds trans to Re-O bonds as in ReO{sub 2}F{sub 4}{sup {minus}} and by the occurrence of both fluorine bridges trans to Re-O bonds. Fluorine-19 NMR spectra show that ReO{sub 2}F{sub 4}{sup {minus}}, Re{sub 2}O{sub 4}F{sub 7}{sup {minus}}, and ReO{sub 2}F{sub 3}(CH{sub 3}CN) have cis-dioxo arrangements in CH{sub 3}CN solution. Density functional theory calculations at the local and nonlocal levels confirm that the cis-dioxo isomers of ReO{sub 2}F{sub 4}{sup {minus}} and ReO{sub 2}F{sub 3}(CH{sub 3}CN), where CH{sub 3}CN is bonded trans to an oxygen, are the energy-minimized structures. The adduct ReO{sub 3}F(CH{sub 3}CN){sub 2}{center_dot}CH{sub 3}CN was obtained by hydrolysis of ReO{sub 2}F{sub 3}(CH{sub 3}CN), and was shown by X-ray crystallography to have a facial arrangement of oxygen atoms on rhenium.« less
  • The reactions in the C{sub 60}-(TiCl{sub 4} + Br{sub 2}) system have been performed in ampoules at elevated temperatures. The molecular structure of the fullerene halides (C{sub 60}Cl{sub 5}){sub 2}, C{sub 60}X{sub 6}, C{sub 60}X{sub 8}, and C{sub 60}X{sub 24} (X = Cl, Br) has been determined and refined using single-crystal X-ray diffraction. It has been established that an increase in the bromine concentration results in an increase in the number of halogen atoms attached to the fullerene cage and in an increase in the relative fraction of bromine atoms in mixed halogen derivatives from almost pure chlorides (C{sub 60}Cl{submore » 5}){sub 2} and C{sub 60}Cl{sub 6} to halides C{sub 60}X{sub 8} and C{sub 60}X{sub 24} with a high relative bromine content.« less
  • The ..mu..-methylene cluster Ru/sub 3/(CO)/sub 7/(..mu..-CH)/..mu../sub 3/-eta/sup 3/-CH/sub 2/=C=C(i-Pr))/(..mu..-PPh/sub 2/) (2) synthesized from Ru/sub 3/-(CO)/sub 8//..mu..=eta/sup 3/-CH/sub 2/=C=C(i-Pr)/(..mu..-PPh/sub 2/) (1) via reaction with diazomethane, CH/sub 2/N/sub 2/, displays a remarkable reactivity associated with the ..mu..-CH/sub 2/ group under mild conditions. Slow isomerization of 2 to the 2-isopropyl-1,3-butadienediyl cluster (..mu..-H)Ru/sub 3/(CO)/sub 7//..mu../sub 3/-eta/sup 4/-CH=C(i-Pr)C=CH/sub 2//(..mu..-PPh/sub 2/) (3) (crystal data: triclinic, space group P anti 1, a = 9.333 (2) A, b = 10.200 (1) A, c = 16.297 (2) A, ..cap alpha.. = 87.25 (1)/sup 0/, ..beta.. = 83.26 (1)/sup 0/, ..gamma.. = 64.29 (1)/sup 0/, Z = 2, R =more » 0.25, R/sub w/ = 0.029 on 5899 observed reflections) occurs under nitrogen. Cluster 3 contains a triangular Ru/sub 3/ core with ..mu..-PPh/sub 2/ and ..mu..-H groups on one edge and a four-carbon hydrocarbyl ligand derived from a CH fragment of the ..mu..-methylene bride and the allenyl ligand of 2. Under an atmosphere of CO and in the presence of methanol complex 2 yields the open allenyl cluster Ru/sub 3/(CO)/sub 9//..mu../sub 3/-eta/sup 3/-CH/sub 2/=C=C(i-Pr)/(..mu..-PPh/sub 2/) (5) and methyl acetate, both of which were characterized spectroscopically.« less