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Title: Anisometric C 60 Fullerene Colloids Assisted by Structure-Directing Agent

Abstract

Colloidal synthesis and assembly provide low cost, large area routes to mesoscale structures. In particular, shape-anisotropic particles may form crystalline, plastic crystalline, complex liquid crystalline and glassy phases. Arrangements in each order class have been used to generate photonic materials. For example, large photonic band gaps have been found for photonic crystals, hyperuniform photonic glasses, and also for plastic crystals at sufficient refractive index contrast. The latter structures support highly isotropic bandgaps that are desirable for free-form waveguides and LED out-coupling. Photonic glasses with optical gain lead to self-tuned lasing by the superposition of multiply scattered light. Typically, extrinsic media such as organic dyes, rare earths, lanthanides and quantum dots are used to impart optical gain in photonic solids. The present work advances fullerene microcrystals as a new materials platform for ‘active’ light emitting in colloid-based photonic crystals. Fullerenes support singlet excited states that recombine to produce a characteristic red photoluminescence. C 60 also has a high refractive index (n ~ 2.2) and transparency (> 560 nm) 9 so that inverse structures are not required.

Authors:
 [1];  [1];  [1];  [1]
  1. Cornell Univ., Ithaca, NY (United States)
Publication Date:
Research Org.:
Cornell Univ., Ithaca, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1283328
Report Number(s):
DOE-Cornell-46517
DOE Contract Number:
FG02-08ER46517
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY

Citation Formats

Penterman, S., Liddell Watson, Chekesha M., Escobedo, Fernando A., and Cohen, Itai. Anisometric C60 Fullerene Colloids Assisted by Structure-Directing Agent. United States: N. p., 2016. Web. doi:10.2172/1283328.
Penterman, S., Liddell Watson, Chekesha M., Escobedo, Fernando A., & Cohen, Itai. Anisometric C60 Fullerene Colloids Assisted by Structure-Directing Agent. United States. doi:10.2172/1283328.
Penterman, S., Liddell Watson, Chekesha M., Escobedo, Fernando A., and Cohen, Itai. Fri . "Anisometric C60 Fullerene Colloids Assisted by Structure-Directing Agent". United States. doi:10.2172/1283328. https://www.osti.gov/servlets/purl/1283328.
@article{osti_1283328,
title = {Anisometric C60 Fullerene Colloids Assisted by Structure-Directing Agent},
author = {Penterman, S. and Liddell Watson, Chekesha M. and Escobedo, Fernando A. and Cohen, Itai},
abstractNote = {Colloidal synthesis and assembly provide low cost, large area routes to mesoscale structures. In particular, shape-anisotropic particles may form crystalline, plastic crystalline, complex liquid crystalline and glassy phases. Arrangements in each order class have been used to generate photonic materials. For example, large photonic band gaps have been found for photonic crystals, hyperuniform photonic glasses, and also for plastic crystals at sufficient refractive index contrast. The latter structures support highly isotropic bandgaps that are desirable for free-form waveguides and LED out-coupling. Photonic glasses with optical gain lead to self-tuned lasing by the superposition of multiply scattered light. Typically, extrinsic media such as organic dyes, rare earths, lanthanides and quantum dots are used to impart optical gain in photonic solids. The present work advances fullerene microcrystals as a new materials platform for ‘active’ light emitting in colloid-based photonic crystals. Fullerenes support singlet excited states that recombine to produce a characteristic red photoluminescence. C60 also has a high refractive index (n ~ 2.2) and transparency (> 560 nm)9 so that inverse structures are not required.},
doi = {10.2172/1283328},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Fri Aug 05 00:00:00 EDT 2016},
month = {Fri Aug 05 00:00:00 EDT 2016}
}

Technical Report:

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  • 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 authors report on the reaction of Ir(CO)Cl(PPh{sub 3}){sub 2}, 1, and C{sub 60}O. The focus here was to investigate the ability of O to direct addition of an iridium compound. The products were separated by liquid chromatography. X-ray diffraction and NMR was used in the characterization of the products. Two epoxide products were produced.
  • The 1990 announcement of the Huffman-Kratschmer fullerene-production technique set off a world-wide explosion of research into the properties and potential applications of C{sub 60} and C{sub 70}. In the last five years, 4,000+ fullerene articles have appeared in the scientific literature dealing with these fascinating molecules and their condensed phases. They possess a complex chemistry reminiscent of the alkenes, and this has led to the syntheses of numerous new compounds and fullerene-based materials, with suggested applications ranging from medicine to photo-conducting polymers to rocket fuel. The work summarized in this report focused on the creation and destruction of fullerene-based materials,more » for the purpose of producing new materials of interest. This three year project was supported by a grant from the Advanced Energy Projects Division, Office of Basic Energy Sciences, U.S. Department of Energy (DE-FG03-93ER12133). Following are outlines of the work completed in each of the three years, a section devoted to the professional and educational development of those involved, a brief section on the outlook for fullerene-based materials, and an appendix listing the publications resulting from this project.« less
  • The homogeneous electrocatalytic reduction of 1,2-dihaloethanes by anions of larger fullerenes, C{sub 76}, C{sub 78}, and C{sub 84}, is presented, and structure-reactivity correlations are derived by including the data reported earlier for the C{sub 60} and C{sub 70} electrocatalytic process. Cyclic voltammetry measurements indicate that dianions of C{sub 76} and C{sub 78}, as well as trianions of C{sub 76}, C{sub 78}, and C{sub 84}, electrochemically generated in 0.1 M (TBA)PF{sub 6}, in benzonitrile, catalyze dehalogenation of 1,2-dihaloethanes. Values of the second-order rate constant, {kappa}, for the electrocatalytic dehalogenation of 1,2-dihaloethanes by the fullerene anions were determined by using the rotating-diskmore » electrode voltammetry under pseudo-first-order conditions with respect to the 1,2-dihaloethanes. For each fullerene anion, {kappa} increases in the order: Cl < Br < 1 for the investigated 1,2-dihaloethanes. Also, log {kappa} linearly increases in the order: C{sub 84} < C{sub 78} < C{sub 76} < C{sub 70} < C{sub 60}, as a function of respective redox potentials of the fullerene, for each 1,2-dihaloethane. Unlike the C{sub 60}{sup n{minus}} electrocatalysis, reported by the authors earlier to be accompanied by chemical reaction between C{sub 60}{sup n{minus}} and certain {alpha},{omega}-diiodoalkanes yielding alkyl adducts of C{sub 60}, no reaction between the anions of larger fullerenes and 1,2-dihaloethanes was observed within the voltammetric time scale. Because of the high stability with respect to adduct formation and more positive potentials of the electrocatalyses, the larger fullerenes may be more useful than C{sub 60} as catalysts, even though the corresponding catalytic rate constants are smaller.« less
  • C{sub 60} is found to dissolve in liquid triphenylantimony. Upon cooling, red crystals form which were characterized by X-ray diffraction and found to be C{sub 60}{center_dot}6SbPh{sub 3}. The quality of the crystals was excellent allowing structural determination without the presence of twinning or orientational disorder.