ACCEPTED MANUSCRIPT
7
7. Pal, S. K.; Itkis, M. E.; Tham, F. S.; Reed, R. W.; Oakley, R. T.;
Haddon, R. C. J. Am. Chem. Soc. 2008, 130, 3942.
8. Pal, S. K.; Itkis, M. E.; Tham, F. S.; Reed, R. W.; Oakley, R. T.;
115.53, 72.30, 39.40, 30.19, 29.07, 23.58, 23.03, 14.15, 11.07.
+
HRMS (MALDI-FTMS) m/z found 1019.5227 (C69H72NaO6
[M+Na]+ cal: 1019.5227).
Donnadieu, B.; Haddon, R. C. J. Am. Chem. Soc.2007, 129, 7163.
9. Koutentis, P. A.; Chen, Y.; Cao, Y.; Best, T. P.; Itkis, M. E.; Beer,
L.; Oakley, R. T.; Cordes, A. W.; Brock, C. P.; Haddon, R. C. J.
Am. Chem. Soc. 2001, 123, 3864.
5,5’,5’’-(1,3,5-Phenylene)tris[1,9-Dithiophenalenylium
chloride ] (23+3Cl-)
10. Beer, L.; Mandal, S. K.; Reed, R. W.; Oakley, R. T.; Tham, F. S.;
Donnadieu, B.; Haddon, R. C. Crystal Growth & Design. 2007, 7,
802.
11. Beer, L.; Reed, R. W.; Robertson, C. M.; Oakley, R. T.; Tham, F.
S.; Haddon, R. C. Org. Lett. 2008, 10, 3121.
P2S5 (667 mg, 3 mmol), Sublimed Sulfur (6 mg, 0.2 mmol)
and Hexamethyldisiloxane (49 mg, 0.3 mmol) was stirred in
toluene (150 ml) at room temperature for 10 min. Then 5,5’,5’’-
(1,3,5-Phenylene)tris[9-(2-ethylhexoxy)-1-oxophenalene]
(8)
12. Sarkar, A.; Pal, S. K.; Itkis, M. E.; Tham, F. S.; Haddon, R. C. J.
(400 mg, 0.4 mmol) dissolved in 1,2-Dichlorobenzene (50 ml)
was added. The mixture were held at 85℃ overnight under Ar,
then cooled to room temperature and filtered. Brown black solid
was obtained and washed twice using toluene. Then the brown
black solid was added to 4M HCl (50 mL) and reflux 2 h under
Ar. After cool to room temperature, the mixture was filtered, the
solid was washed using distilled water, acetone and methylene
chloride. After vacuum dryness, brown solid was formed (507
mg). Without further treatment, the solid was used directely next
step.
Mater. Chem. 2012, 22, 8245.
13. Sarkar, A.; Tham, F. S.; Haddon, R. C. J. Mater. Chem. 2011,
21.1574
14. Goto, K.; Kubo, T.; Yamamoto, K.; Nakasuji, K.; Sato, K.;
Shiomi, D.; Takui, T.; Kubota, M.; Kobayashi, T.; Yakusi, K.;
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Naito, A.; Takui, T.; Nakasuji, K. Angew. Chem. Int. Ed. 2002, 41,
1793.
16. Morita, Y.; Ohba, T.; Haneda, N.; Maki, S.; Kawai, J.; Hatanaka,
K.; Sato, K.; Shiomi, D.; Takui, T.; Nakasuji, K. J. Am. Chem.
Soc. 2000, 122, 4825.
17. Hou, Y.; Wang, H.; Li, Z.; Liu, Y.; Wan, X.; Xue, X.; Chen, Y.;
Yu, A. Tetrahedron Lett. 2011, 52, 3670.
18. Nakasuji, K.; Yoshida, K.; Murata, I. J. Am. Chem. Soc. 1982,
104, 1432.
19. Ohashi, K.; Kubo, T.; Masui, T.; Yamamoto, K.; Nakasuji, K.;
Takui, T.; Kai, Y.; Murata, I. J. Am. Chem. Soc. 1998, 120, 2018.
20. Bag, P; Tham, F. S; Donnadieu, B; Haddon. R. C. Org. Lett. 2013,
15, 1198.
21. Zhang, L; Fakhouri, S.M; Liu, F; Timmons, J. C; Ran, N. A;
Briseno, A.L. J. Mater. Chem., 2011, 21, 1329–1337.
22. Mochida, T.; Suzuki, S.; Takasu, I.; Sugawara, T. J. Phys.
Chem.Solids. 2003, 64, 1257.
23. Chi, X.; Itkis, M. E.; Patrick, B. O.; Barclay, T. M.; Reed, R. W.;
Oakley, R. T.; Cordes, A. W.; Haddon, R. C. J. Am. Chem. Soc.
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24. Chi, X.; Itkis, M. E.; Reed, R. W.; Oakley, R. T.; Cordes, A. W.;
Haddon, R. C. J. Phys. Chem. B. 2002, 106, 8278.
25. Pal, S. K.; Itkis, M. E.; Reed, R. W.; Oakley, R. T.; Cordes, A.
W.; Tham, F. S.; Siegrist, T.; Haddon, R. C. J. Am. Chem. Soc.
2004, 126, 1478.
5,5’,5’’-(1,3,5-Phenylene)tris{1,9-Dithiophenalenylium
tetrakis[(3,5-trifluoromethyl)phenyl] borate] (23+3TFPB-)
Compound 23+3Cl- (507 mg) and sodium tetrakis[3,5-
bis(trifluoromethyl)phenyl]borate (NaTFPB) (1.44 g, 1.6 mmol)
were stirred in dry methylene chloride under Ar at room
temperature for 10 h. Filtered and solid was washed twice using
methylene chloride. The filtrate was evaporated to dryness under
reduced pressure to give a brown solid, which was purified by
recrystallization from methylene chloride under -60℃. After the
impurity was filtered, the filtrate was evaporated to give a golden
1
solide (896 mg, yield 62%). H NMR (300M, CD3COCD3)
δ
9.89 (s, 2H), 9.44 (d, J=9.0, 2H), 9.30 (d, J=9.0, 2H), 9.11 (s,
1H), 7.78 (m, 8H), 7.67 (s, 4H). 13C NMR (100M, CD3COCD3)
δ 168.65, 162.62 (q), 143.43, 142.64, 141.24, 135.56, 130.80,
130.27, 129.81, 129.48, 127.20, 125.37, 123.60, 119.99, 118.45.
HRMS (MALDI-FTMS) m/z 752.9965 (C45H21S6 [M]+ cal:
m/z=752.9967).
26. Mandal, S. K.; Itkis, M. E.; Chi, X.; Samanta, S.; Lidsky, D.;
Reed, R. W.; Oakley, R. T.; Tham, F. S.; Haddon, R. C. J. Am.
Chem. Soc. 2005, 127, 8185.
27. Mandal, S. K.; Samanta, S.; Itkis, M. E.; Jensen, D. W.; Reed, R.
W.; Oakley, R. T.; Tham, F. S.; Donnadieu, B.; Haddon, R. C. J.
Am. Chem. Soc. 2006, 128, 1982.
28. Sarkar, A.; Pal, S. K.; Itkis, M. E.; Liao, P.; Tham, F. S.;
Donnadieu, B.; Haddon, R. C. Chem.Mater. 2009, 21, 2226.
29. Li, Y.; Heng, W.-K.; Lee, B. S.; Aratani, N.; Zafra, J. L.; Bao, N.;
Lee, R.; Sung, Y. M.; Sun, Z.; Huang, K.-W.; Webster, R. D.;
López Navarrete, J. T.; Kim, D.; Osuka, A.; Casado, J.; Ding, J.;
Wu, J. J. Am. Chem. Soc. 2012, 134, 14913.
30. Sun, Z.; Wu, J. J. Mater. Chem. 2012, 22, 4151.
31. Pisani, L.; Chan, J. A.; Montanari, B.; Harrison, N. M. Phys. Rev.
B. 2007, 75, 064418.
Acknowledgments
The authors gratefully acknowledge financial support from the
NSFC
(Grants
50933003
and
51273093),
MOST
(Grants 2012CB933401 and 2011DFB50300) and NSF of Tianjin
City (Grant 10ZCGHHZ00600).
Supplementary Material
1H NMR, 13C NMR and MS for compounds of 3, 7 and
23+3TFPB-. Solubility of 23+ salt with different anions and other
information.
32. Wang, Y.; Huang, Y.; Song, Y.; Zhang, X.; Ma, Y.; Liang, J.;
Chen, Y. Nano. Lett. 2008, 9, 220.
33. Ning, G.; Xu, C.; Hao, L.; Kazakova, O.; Fan, Z.; Wang, H.;
Wang, K.; Gao, J.; Qian, W.; Wei, F. Carbon. 2013, 51, 390.
34. Fernández-Rossier, J.; Palacios, J. J. Phys. Rev. Lett. 2007, 99,
177204.
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