Citation: Xin Hanshen, Ge Congwu, Fu Lina, Yang Xiaodi, Gao Xike. Naphthalene Diimides Endcapped with Ethynylazulene: Molecular Design, Synthesis and Properties[J]. Chinese Journal of Organic Chemistry, ;2017, 37(3): 711-719. doi: 10.6023/cjoc201609029 shu

Naphthalene Diimides Endcapped with Ethynylazulene: Molecular Design, Synthesis and Properties

Xin Hanshen ^a ,
Ge Congwu ^a ,
Fu Lina ^a,b ,
Yang Xiaodi ^c ,
Gao Xike ^a,*,,

a.
Key Laboratory of Synthetic and Self-Assembly Chemistry for Organic Functional Molecules, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032
b.
School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237
c.
Laboratory of Advanced Materials, Fudan University, Shanghai 200433

Corresponding author: Gao Xike, gaoxk@mail.sioc.ac.cn
Received Date: 27 September 2016
Revised Date: 25 October 2016

Fund Project: the Shanghai Science and Technology Committee 16JC1400603the National Natural Science Foundation of China 21522209the " Strategic Priority Research Program" XDB12010100

Figures(7)

Azulene is noteworthy for its deep blue color with a large dipole moment. Compared to other unsaturated aromatic hydrocarbons, azulenes show unique photophysical and electrical properties. Herein, two isomers of 1, 4, 5, 8-naphthalene diimide (NDI) endcapped with ethynylazulene units (1 and 2) are presented, which are capped with five-membered and seven-membered rings of azulene moieties, respectively. It is interesting that these two compounds show remarkably different physicochemical properties, thermal stabilities and organic field-effect transistors (OFET) performance resulting from the different connections of an electron-rich five-membered ring and an electron-poor seven-membered ring. Density functional theory (DFT) calculations reveal that the lowest unoccupied molecular orbital (LUMO) energy of 2 (endcapped with 6-ethynylalzulene) is lower than that of 1 (endcapped with 2-ethynylalzulene), and 2 makes the electrons of LUMO more delocalized, which favor the overlap of LUMO between molecules, thus to obtain higher mobility for 2. OFETs based on thin films of these two isomers were fabricated with conventional spin-coated techniques. Under nitrogen atmosphere, 1 and 2 show n-type semiconducting properties with electron mobilities of up to 0.022 and 0.16 cm²·V^-1·s^-1, respectively, which is consistent with the DFT results.
- azulene,
- naphthalene diimide,
- isomer,
- organic field-effect transistors,
- mobility
1. [1]
  Lemal, D. M.; Goldman, G. D. J. Chem. Educ. 1988, 65, 923. doi: 10.1021/ed065p923
2. [2]
  Michl, J.; Thulstrup, E. W. Tetrahedron 1976, 32, 205. doi: 10.1016/0040-4020(76)87002-0
3. [3]
4. [4]
  Dong, J. X.; Zhang, H. L. Chin. Chem. Lett. 2016, 27, 1097. doi: 10.1016/j.cclet.2016.05.005
5. [5]
  Ito, S.; Inabe, H.; Morita, N.; Ohta, K.; Kitamura, T.; Imafuku, K. J. Am. Chem. Soc. 2003, 125, 1669. doi: 10.1021/ja0209262
6. [6]
  (a) Salman, H.; Abraham, Y.; Tal, S.; Meltzman, S.; Kapon, M.; Tessler, N.; Speiser, S.; Eichen, Y. Eur. J. Org. Chem. 2005, 2207.
  (b) Zielinski, T.; Kedziorek, M. J.; Jurczak, J. Chem.-Eur. J. 2008, 14, 838.
7. [7]
  (a) Wang, X.; Ng, J. K.-P.; Jia, P.; Lin, T.; Cho, C. M.; Xu, J.; Lu, X.; He, C. Macromolecules 2009, 42, 5534.
  (b) Amir, E.; Amir, R. J.; Campos, L. M.; Hawker, C. J. J. Am. Chem. Soc. 2011, 133, 10046.
  (c) Koch, M.; Blacque, O.; Venkatesan, K. Org. Lett. 2012, 14, 1580.
  (d) Murai, M.; Amir, E.; Amir, R. J.; Hawker, C. J. Chem. Sci. 2012, 3, 2721.
  (e) Ghazvini Zadeh, E. H.; Tang, S.; Woodward, A. W.; Liu, T.; Bondar, M. V.; Belfield, K. D. J. Mater. Chem. C 2015, 3, 8495.
  (f) Murai, M.; Takami, K.; Takeshima, H.; Takai, K. Org. Lett. 2015, 17, 1798.
8. [8]
  (a) Wang, F. K.; Lai, Y. H.; Kocherginsky, N. M.; Kosteski, Y. Y. Org. Lett. 2003, 5, 995.
  (b) Wang, F. K.; Lai, Y. H.; Han, M. Y. Macromolecules 2004, 37, 3222.
9. [9]
  Cristian, L.; Sasaki, I.; Lacroix, P. G.; Donnadieu, B.; Asselberghs, I.; Clays, K.; Razus, A. C. Chem. Mater. 2004, 16, 3543. doi: 10.1021/cm0492989
10. [10]
  (a) Kurotobi, K.; Kim, K. S.; Noh, S. B.; Kim, D.; Osuka, A. Angew. Chem., Int. Ed. 2006, 45, 3944.
  (b) Wang, F. K.; Lin, T. T.; He, C. B.; Chi, H.; Tang, T.; Lai, Y. H. J. Mater. Chem. 2012, 22, 10448.
  (c) Ince, M.; Bartelmess, J.; Kiessling, D.; Dirian, K.; Martinez-Diaz, M. V.; Torres, T.; Guldi, D. M. Chem. Sci. 2012, 3, 1472.
11. [11]
  (a) Yamaguchi, Y.; Maruya, Y.; Katagiri, H.; Nakayama, K.; Ohba, Y. Org. Lett. 2012, 14, 2316.
  (b) Yamaguchi, Y.; Ogawa, K.; Nakayama, K.; Ohba, Y.; Katagiri, H. J. Am. Chem. Soc. 2013, 135, 19095.
  (c) Yao, J. J.; Cai, Z. X.; Liu, Z. T.; Yu, C. M.; Luo, H. W.; Yang, Y.; Yang, S. F.; Zhang, G. X.; Zhang, D. Q. Macromolecules 2015, 48, 2039.
12. [12]
  Puodziukynaite, E.; Wang, H. W.; Lawrence, J.; Wise, A. J.; Russell, T. P.; Barnes, M. D.; Emrick, T. J. Am. Chem. Soc. 2014, 136, 11043. doi: 10.1021/ja504670k
13. [13]
  Nishimura, H.; Ishida, N.; Shimazaki, A.; Wakamiya, A.; Saeki, A.; Scott, L. T.; Murata, Y. J. Am. Chem. Soc. 2015, 137, 15656. doi: 10.1021/jacs.5b11008
14. [14]
  Xin, H. S.; Ge, C. W.; Yang, X. D.; Gao, H. L.; Yang, X. C.; Gao, X. K. Chem. Sci. 2016, 7, 6701. doi: 10.1039/C6SC02504H
15. [15]
  (a) Lokey, R. S.; Iverson, B. L. Nature 1995, 375, 303.
  (b) Zych, A. J.; Iverson, B. L. J. Am. Chem., Soc. 2000, 122, 8898.
  (c) Pantoş, G. D.; Pengo, P.; Sanders, J. K. M. Angew. Chem. Int. Ed. 2007, 46, 194.
16. [16]
  (a) Redmore, N. P.; Rubtsov, I. V.; Therien, M. J. J. Am. Chem. Soc. 2003, 125, 8769.
  (b) Kelley, R. F.; Tauber, M. J.; Wasielewski, M. R. J. Am. Chem. Soc. 2006, 128, 4779.
  (c) Reczek, J. J.; Villazor, K. R.; Lynch, V.; Swager, T. M.; Iverson, B. L. J. Am. Chem. Soc. 2006, 128, 7995.
17. [17]
  (a) Takenaka, S.; Yamashita, K.; Takagi, M.; Uto, Y.; Kondo, H. Anal. Chem. 2000, 72, 1334.
  (b) Rogers, J. E.; Weiss, S. J.; Kelly, L. A. J. Am. Chem. Soc. 2000, 122, 427.
  (c) Abraham, B.; McMasters, S.; Mullan, M. A.; Kelly, L. A. J. Am. Chem. Soc. 2004, 126, 4293.
18. [18]
  Miller, L. L.; Mann, K. R. Acc. Chem. Res. 1996, 29, 417. doi: 10.1021/ar9600446
19. [19]
  (a) Katz, H. E.; Lovinger, A. J.; Johnson, J.; Kloc, C.; Siegrist, T.; Li, W.; Lin, Y.-Y.; Dodabalapur, A. Nature 2000, 404, 478.
  (b) Würthner, F. Angew. Chem., Int. Ed. 2001, 40, 1037.
  (c) Jones, B. A.; Facchetti, A.; Wasielewski, M. R.; Marks, T. J. J. Am. Chem. Soc. 2007, 129, 15259.
20. [20]
  (a) Gao, X. K.; Di, C. A.; Hu, Y. B.; Yang, X. D.; Fan, H. Y.; Zhang, F.; Liu, Y. Q.; Li, H. X.; Zhu, D. B. J. Am. Chem. Soc. 2010, 132, 3697.
  (b) Hu, Y. B.; Gao, X. K.; Di, C. A.; Yang, X. D.; Zhang, F.; Liu, Y. Q.; Li, H. X.; Zhu, D. B. Chem. Mater. 2011, 23, 1204.
  (c) Zhang, F.; Hu, Y.; Schuettfort, T.; Di, C. A.; Gao, X.; McNeill, C. R.; Thomsen, L. S.; Mannsfeld, C.; Yuan, W.; Sirringhaus, H.; Zhu, D. B. J. Am. Chem. Soc. 2013, 135, 2338.
  (d) Hu, Y. B.; Wang, Z. L.; Zhang, X.; Yang, X. D.; Li, H. X.; Gao, X. K. Chin. J. Chem. 2013, 31, 1428.
21. [21]
  Chang, J.; Ye, Q.; Huang, K.; Zhang, J. Chen, Z.; Wu, J.; Chi, C. Org. Lett. 2012, 14, 2964. doi: 10.1021/ol300914k
22. [22]
  Li, Y. H.; Zhang, G. X.; Zhang, W.; Wang, J. G.; Chen, X.; Liu, Z. T.; Yan, Y. L.; Zhao, Y. S.; Zhang, D. Q. Chem. Asian J. 2014, 9, 3207. doi: 10.1002/asia.201402768
23. [23]
  (a) Zhang, J.; Petoud, S.Chem. Eur. J.2008, 14, 1264.
  (b) Nozoe, T.; Takase, K.; Shimazaki, N. Bull. Chem. Soc. Jpn.1964, 37, 1644.
  (c) Takase, K.; Asao, T.; Takagi, Y.; Nozoe, T. Chem. Commun. (London)1968, 368b.
  (d) McDonald, R. N.; Richmond, J. M.; Curtis, J. R.; Petty, H. E.; Hoskins, T. L. J. Org. Chem. 1976, 41, 1811.
  (e) Koch, M.; Blacque, O.; Venkatesan, K. Org. Lett. 2012, 14, 1580.
  (f) Nozoe, T.; Seto, S.; Matsumura, S.; Murase, Y. Bull. Chem. Soc. Jpn.1962, 35, 1179.
  (g) Ito, S.; Inabe, H.; Okujima, T.; Morita, N.; Watanabe, M.; Harada, N.; Imafuku, K. J. Org. Chem.2001, 66, 7090.
24. [24]
  Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H. Vreven, T.; Montgomery, J. A.; Jr., Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, Ö.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian 09, Revision A.02, Gaussian, Inc, Wallingford CT, 2009.
25. [25]
  Mishra, A.; Behera, R. K.; Behera, P. K.; Mishra, B. K.; Behera, G. B. Chem. Rev. 2000, 100, 1973. doi: 10.1021/cr990402t
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