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Title: A faux hawk fullerene with PCBM-like properties

Journal Article · · Chemical Science (Online)
DOI:https://doi.org/10.1039/C4SC02970D· OSTI ID:1171261
 [1];  [1];  [2];  [1];  [3];  [4];  [4];  [5];  [6];  [3];  [1];  [1]
  1. Colorado State Univ., Fort Collins, CO (United States)
  2. Colorado State Univ., Fort Collins, CO (United States); National Renewable Energy Lab. (NREL), Golden, CO (United States)
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  4. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  5. Leibniz Inst. for Solid State and Materials Research (IFW), Dresden (Germany)
  6. Univ. of Chicago Advanced Photon Source, Argonne, IL (United States)
+ Show Author Affiliations

Reaction of C60, C6F5CF2I, and SnH(n-Bu)3 produced, among other unidentified fullerene derivatives, the two new compounds 1,9-C60(CF2C6F5)H (1) and 1,9-C60(cyclo-CF2(2-C6F4)) (2). The highest isolated yield of 1 was 35% based on C60. Depending on the reaction conditions, the relative amounts of 1 and 2 generated in situ were as high as 85% and 71%, respectively, based on HPLC peak integration and summing over all fullerene species present other than unreacted C60. Compound 1 is thermally stable in 1,2-dichlorobenzene (oDCB) at 160 °C but was rapidly converted to 2 upon addition of Sn2(n-Bu)6 at this temperature. In contrast, complete conversion of 1 to 2 occurred within minutes, or hours, at 25 °C in 90/10 (v/v) PhCN/C6D6 by addition of stoichiometric, or sub-stoichiometric, amounts of proton sponge (PS) or cobaltocene (CoCp2). DFT calculations indicate that when 1 is deprotonated, the anion C60(CF2C6F5)- can undergo facile intramolecular SNAr annulation to form 2 with concomitant loss of F-. To our knowledge this is the first observation of a fullerene-cage carbanion acting as an SNAr nucleophile towards an aromatic C–F bond. The gas-phase electron affinity (EA) of 2 was determined to be 2.805(10) eV by low-temperature PES, higher by 0.12(1) eV than the EA of C60 and higher by 0.18(1) eV than the EA of phenyl-C61-butyric acid methyl ester (PCBM). In contrast, the relative E1/2(0/-) values of 2 and C60, -0.01(1) and 0.00(1) V, respectively, are virtually the same (on this scale, and under the same conditions, the E1/2(0/-) of PCBM is -0.09 V). Time-resolved microwave conductivity charge-carrier yield x mobility values for organic photovoltaic active-layer-type blends of 2 and poly-3-hexylthiophene (P3HT) were comparable to those for equimolar blends of PCBM and P3HT. The structure of solvent-free crystals of 2 was determined by single-crystal X-ray diffraction. The number of nearest-neighbor fullerene–fullerene interactions with centroid∙∙∙centroid (⊙∙∙∙⊙) distances of ≤ 10.34 Å is significantly greater, and the average ⊙∙∙∙⊙ distance is shorter, for 2 (10 nearest neighbors; ave. ⊙∙∙∙⊙ distance = 10.09 Å) than for solvent-free crystals of PCBM (7 nearest neighbors; ave. ⊙∙∙∙⊙ distance = 10.17 Å). Finally, the thermal stability of 2 was found to be far greater than that of PCBM.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS); National Renewable Energy Laboratory (NREL), Golden, CO (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-06CH11357; AC36-08GO28308; AC05-76RL01830
OSTI ID:
1171261
Alternate ID(s):
OSTI ID: 1184288; OSTI ID: 1220716
Report Number(s):
PNNL-SA-105706; NREL/JA-5900-64001
Journal Information:
Chemical Science (Online), Vol. 6, Issue 3; ISSN 2041-6539
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
ENGLISH
Citation Metrics:
Cited by: 8 works
Citation information provided by
Web of Science

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Cited By (2)

Fluorous Fullerene Acceptors in Vacuum‐Deposited Photovoltaic Cells journal May 2019
Doped N‐Type Organic Field‐Effect Transistors Based on Faux‐Hawk Fullerene journal May 2019

Linked Research (1)

Figures / Tables (15)

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
36 MATERIALS SCIENCE
nucleophilic aromatic substitution
heptafluorobenzyl
perfluorobenzyl
fullerene
hydrofullerene
electron affinity
DFT
OPV
organic photovoltaic
time-resolved microwave conductivity
X-ray crystallography
PCBM
Environmental Molecular Sciences Laboratory
14 SOLAR ENERGY
77 NANOSCIENCE AND NANOTECHNOLOGY
fullerene derivatives