A faux hawk fullerene with PCBM-like properties

Long K. San, Eric V. Bukovsky, Bryon W. Larson, James B. Whitaker, S. H M Deng, Nikos Kopidakis, Gary Rumbles, Alexey A. Popov, Yu Sheng Chen, Xue Bin Wang, Olga V. Boltalina, Steven H. Strauss

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

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 × 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 (o⋯o) distances of ≤10.34 Å is significantly greater, and the average o⋯o distance is shorter, for 2 (10 nearest neighbors; ave. o⋯o distance = 10.09 Å) than for solvent-free crystals of PCBM (7 nearest neighbors; ave. o⋯o distance = 10.17 Å). Finally, the thermal stability of 2 was found to be far greater than that of PCBM.

Original languageEnglish
Pages (from-to)1801-1815
Number of pages15
JournalChemical Science
Volume6
Issue number3
DOIs
Publication statusPublished - Mar 1 2015

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Fullerenes
Butyric Acid
Esters
Electron affinity
Crystals
Nucleophiles
Charge carriers
Discrete Fourier transforms
Anions
Protons
Thermodynamic stability
Gases
Microwaves
Single crystals
Derivatives
X ray diffraction
Temperature

ASJC Scopus subject areas

  • Chemistry(all)

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San, L. K., Bukovsky, E. V., Larson, B. W., Whitaker, J. B., Deng, S. H. M., Kopidakis, N., ... Strauss, S. H. (2015). A faux hawk fullerene with PCBM-like properties. Chemical Science, 6(3), 1801-1815. https://doi.org/10.1039/c4sc02970d

A faux hawk fullerene with PCBM-like properties. / San, Long K.; Bukovsky, Eric V.; Larson, Bryon W.; Whitaker, James B.; Deng, S. H M; Kopidakis, Nikos; Rumbles, Gary; Popov, Alexey A.; Chen, Yu Sheng; Wang, Xue Bin; Boltalina, Olga V.; Strauss, Steven H.

In: Chemical Science, Vol. 6, No. 3, 01.03.2015, p. 1801-1815.

Research output: Contribution to journalArticle

San, LK, Bukovsky, EV, Larson, BW, Whitaker, JB, Deng, SHM, Kopidakis, N, Rumbles, G, Popov, AA, Chen, YS, Wang, XB, Boltalina, OV & Strauss, SH 2015, 'A faux hawk fullerene with PCBM-like properties', Chemical Science, vol. 6, no. 3, pp. 1801-1815. https://doi.org/10.1039/c4sc02970d
San LK, Bukovsky EV, Larson BW, Whitaker JB, Deng SHM, Kopidakis N et al. A faux hawk fullerene with PCBM-like properties. Chemical Science. 2015 Mar 1;6(3):1801-1815. https://doi.org/10.1039/c4sc02970d
San, Long K. ; Bukovsky, Eric V. ; Larson, Bryon W. ; Whitaker, James B. ; Deng, S. H M ; Kopidakis, Nikos ; Rumbles, Gary ; Popov, Alexey A. ; Chen, Yu Sheng ; Wang, Xue Bin ; Boltalina, Olga V. ; Strauss, Steven H. / A faux hawk fullerene with PCBM-like properties. In: Chemical Science. 2015 ; Vol. 6, No. 3. pp. 1801-1815.
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abstract = "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 × 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 (o⋯o) distances of ≤10.34 {\AA} is significantly greater, and the average o⋯o distance is shorter, for 2 (10 nearest neighbors; ave. o⋯o distance = 10.09 {\AA}) than for solvent-free crystals of PCBM (7 nearest neighbors; ave. o⋯o distance = 10.17 {\AA}). Finally, the thermal stability of 2 was found to be far greater than that of PCBM.",
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T1 - A faux hawk fullerene with PCBM-like properties

AU - San, Long K.

AU - Bukovsky, Eric V.

AU - Larson, Bryon W.

AU - Whitaker, James B.

AU - Deng, S. H M

AU - Kopidakis, Nikos

AU - Rumbles, Gary

AU - Popov, Alexey A.

AU - Chen, Yu Sheng

AU - Wang, Xue Bin

AU - Boltalina, Olga V.

AU - Strauss, Steven H.

PY - 2015/3/1

Y1 - 2015/3/1

N2 - 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 × 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 (o⋯o) distances of ≤10.34 Å is significantly greater, and the average o⋯o distance is shorter, for 2 (10 nearest neighbors; ave. o⋯o distance = 10.09 Å) than for solvent-free crystals of PCBM (7 nearest neighbors; ave. o⋯o distance = 10.17 Å). Finally, the thermal stability of 2 was found to be far greater than that of PCBM.

AB - 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 × 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 (o⋯o) distances of ≤10.34 Å is significantly greater, and the average o⋯o distance is shorter, for 2 (10 nearest neighbors; ave. o⋯o distance = 10.09 Å) than for solvent-free crystals of PCBM (7 nearest neighbors; ave. o⋯o distance = 10.17 Å). Finally, the thermal stability of 2 was found to be far greater than that of PCBM.

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