Citation: Xuan Zhang, Xu-Dong Li. Effect of the position of substitution on the electronic properties of nitrophenyl derivatives of fulleropyrrolidines：Fundamental understanding toward raising LUMO energy of fullerene electron-acceptor[J]. Chinese Chemical Letters, ;2014, 25(4): 501-504. doi: 10.1016/j.cclet.2013.11.050 shu

Effect of the position of substitution on the electronic properties of nitrophenyl derivatives of fulleropyrrolidines：Fundamental understanding toward raising LUMO energy of fullerene electron-acceptor

Xuan Zhang ^, ,
Xu-Dong Li

1.
College of Chemistry, Chemical Engineering & Biotechnology, Donghua University, Shanghai 201620, China

Corresponding author: Xuan Zhang,
Received Date: 24 October 2013
Available Online: 22 November 2013
Fund Project: This work was financially supported by Shanghai Pujiang Program (No. 11PJ1400200) (No. 11PJ1400200) Innovation Program of Shanghai Municipal Education Commission (No. 12ZZ067) (No. 12ZZ067)

A series of substituted para-, meta- and ortho-nitrophenyl derivatives of fulleropyrrolidine were synthesized to investigate the effects of the position of substitution on electronic properties by using steady-state absorption and fluorescence spectra, combined with DFT calculations. The results confirmed that the position of substitution has little effect on absorption and fluorescence spectra, whereas a significant effect was observed on their LUMO energy levels. The theoretical calculations revealed that the LUMO energy of the ortho-nitrophenyl substituted derivative was increased 0.1 eV above those of para- and meta-substitution. The prominent effect of ortho-substitution was attributed to the through-space orbital interaction between spatially closed electron-withdrawing nitro group and fullerene cage. These findings could provide fundamental insights in raising LUMO levels of C₆₀-based electron acceptor materials and an alternative strategy to increase open circuit voltage V_oc in polymer solar cells.
- Fullerene,
- Substituent effect,
- Orbital interaction,
- Organic photovoltaics
1. [1]
  [1] H.W. Kroto, J.R. Heath, S.C. O'Brien, R.F. Curl, R.E. Smalley, C60: Buckminsterfullerene, Nature 318 (1985) 162-163.
2. [2]
  [2] D.M. Guldi, Fullerenes: three dimensional electron acceptor materials, Chem. Commun. (2000) 321-327.
3. [3]
  [3] D.M. Guldi, B.M. Illescas, C.M. Atienza, M. Wielopolski, N. Martín, Fullerene for organic electronics, Chem. Soc. Rev. 38 (2009) 1587-1597.
4. [4]
  [4] G. Li, R. Zhu, Y. Yang, Polymer solar cells, Nat. Photonics 6 (2012) 153-161.
5. [5]
  [5] B.C. Thompson, J.M.J. Fréchet, Polymer-fullerene composite solar cells, Angew. Chem. Int. Ed. 47 (2008) 58-77.
6. [6]
  [6] G. Dennler, M.C. Scharber, C.J. Brabec, Polymer-fullerene bulk-heterojunction solar cells, Adv. Mater. 21 (2009) 1323-1338.
7. [7]
  [7] D. Jariwala, V.K. Sangwan, L.J. Lauhon, T.J. Marks, M.C. Hersam, Carbon nanomaterials for electronics, optoelectronics, photovoltaics, and sensing, Chem. Soc. Rev. 42 (2013) 2824-2860.
8. [8]
  [8] J.B. You, L.T. Dou, K. Yoshimura, et al., A polymer tandem solar cell with 10.6% power conversion efficiency, Nat. Commun. 4 (2013) 1446.
9. [9]
  [9] C.J. Brabec, A. Cravino, D. Meissner, et al., Origin of the open circuit voltage of plastic solar cells, Adv. Funct. Mater. 11 (2001) 374-380.
10. [10]
  [10] M.C. Scharber, D. Wühlbacher, M. Koppe, et al., Design rules for donors in bulkheterojunction solar cells - towards 10% energy-conversion efficiency, Adv. Mater. 18 (2006) 789-794.
11. [11]
  [11] Y.F. Li, Molecular design of photovoltaic materials for polymer solar cells: toward suitable electronic energy levels and broad absorption, Acc. Chem. Res. 45 (2012) 723-733.
12. [12]
  [12] F.B. Kooistra, J. Knol, F. Kastenberg, et al., Increasing the open circuit voltage of bulk-heterojunction solar cells by raising the LUMO level of the acceptor, Org.
13. [13]
  [13] Y.J. He, H.Y. Chen, J.H. Hou, Y.F. Li, Indene-C60 bisadduct: a new acceptor for highperformance polymer solar cells, J. Am. Chem. Soc. 132 (2010) 1377-1382.
14. [14]
  [14] C.L. Chochos, N. Tagmatarchis, V.G. Gregoriou, Rational design on n-type organic materials for high performance organic photovoltaics, RSC Adv. 3 (2013) 7160-7181.
15. [15]
  [15] H.Y. Chen, J. Hou, S. Zhang, et al., Polymer solar cells with enhanced open-circuit voltage and efficiency, Nat. Photonics 3 (2009) 649-653.
16. [16]
  [16] C. Liu, Y.J. Li, C.H. Li, et al., New methanofullerenes containing amide as electron acceptor for construction photovoltaic devices, J. Phys. Chem. C 113 (2009) 21970-21975.
17. [17]
  [17] C. Liu, S.Q. Xiao, X.P. Shu, et al., Synthesis and photovoltaic properties of novel monoadducts and bisadducts based on amide methanofullerene, ACS Appl. Mater. Interfaces 4 (2012) 1065-1071.
18. [18]
  [18] Y. Matsuo, Design concept for high-LUMO-level fullerene electron-acceptors for organic solar cells, Chem. Lett. 41 (2012) 754-759.
19. [19]
  [19] F. Matsumoto, T. Iwai, K. Moriwaki, et al., Design of fullerene derivatives for stabilizing LUMO energy using donor groups placed in spatial proximity to the C60 cage, J. Org. Chem. 77 (2012) 9038-9043.
20. [20]
  [20] Y. Numata, Y. Tajima, J. Kawashima, The substituent effect to the reduction potentials of heterocycle-fused [60] fullerene derivatives, in: 214th ECS Meeting, 2008, Abstract #2719.
21. [21]
  [21] R.F. Peng, B. Jin, K. Cao, et al., Study on the synthetic technology of nitrofulleropyrrolidine, Chinese J. Org. Chem. 27 (2007) 276-278.
22. [22]
  [22] M.J. Frisch, G.W. Trucks, H.B. Schlegel, et al., Gaussian 09, Revision C.01, Gaussian, Inc., Wallingford, CT, 2010.
23. [23]
  [23] H. Wang, Y.J. He, Y.F. Li, et al., Photophysical and electronic properties of five PCBM-like C60 derivatives: spectral and quantum chemical view, J. Phys. Chem. A 116 (2012) 255-262.
24. [24]
  [24] R. Koeppe, N.S. Sariciftci, Photoinduced charge and energy transfer involving fullerene derivatives, Photochem. Photobiol. Sci. 5 (2006) 1122-1131.
25. [25]
  [25] G.D. Han, W.R. Collins, T.L. Andrew, et al., Cyclobutadiene-C60 adducts: n-type materials for organic photovoltaic cells with high Voc, Adv. Funct. Mater. 23 (2013) 3061-3069.
1. [1]
  Zhongjie Li , Xiangyue Kong , Yuhao Liu , Huayu Qiu , Lingling Zhan , Shouchun Yin . Progress of additives for morphology control in organic photovoltaics. Chinese Chemical Letters, 2024, 35(6): 109378-. doi: 10.1016/j.cclet.2023.109378
2. [2]
  Kang Wei , Jiayu Li , Wen Zhang , Bing Yuan , Ming-De Li , Pingwu Du . A strained π-extended [10]cycloparaphenylene carbon nanoring. Chinese Chemical Letters, 2024, 35(5): 109055-. doi: 10.1016/j.cclet.2023.109055
3. [3]
  Nianqiang Jiang , Yiqiang Ou , Yanpeng Zhu , Dingyong Zhong , Jiaobing Wang . Assembly of fullerenes using a highly preorganized janusarene. Chinese Chemical Letters, 2025, 36(4): 110004-. doi: 10.1016/j.cclet.2024.110004
4. [4]
  Jiaxun Wu , Mingde Li , Li Dang . The R eaction of Metal Selenium Complexes with Olefins as a Tutorial Case Study for Analyzing Molecular Orbital Interaction Modes. University Chemistry, 2025, 40(3): 108-115. doi: 10.12461/PKU.DXHX202405098
5. [5]
  Zhimin Sun , Xin-Hui Guo , Yue Zhao , Qing-Yu Meng , Li-Juan Xing , He-Lue Sun . Dynamically switchable porphyrin-based molecular tweezer for on−off fullerene recognition. Chinese Chemical Letters, 2024, 35(6): 109162-. doi: 10.1016/j.cclet.2023.109162
6. [6]
  Wenxiang Ma , Xinyu He , Tianyi Chen , De-Li Ma , Hongzheng Chen , Chang-Zhi Li . Near-infrared non-fused electron acceptors for efficient organic photovoltaics. Chinese Chemical Letters, 2024, 35(4): 109099-. doi: 10.1016/j.cclet.2023.109099
7. [7]
  Min Chen , Boyu Peng , Xuyun Guo , Ye Zhu , Hanying Li . Polyethylene interfacial dielectric layer for organic semiconductor single crystal based field-effect transistors. Chinese Chemical Letters, 2024, 35(4): 109051-. doi: 10.1016/j.cclet.2023.109051
8. [8]
  Jaeyong Ahn , Zhenping Li , Zhiwei Wang , Ke Gao , Huagui Zhuo , Wanuk Choi , Gang Chang , Xiaobo Shang , Joon Hak Oh . Surface doping effect on the optoelectronic performance of 2D organic crystals based on cyano-substituted perylene diimides. Chinese Chemical Letters, 2024, 35(9): 109777-. doi: 10.1016/j.cclet.2024.109777
9. [9]
  Jian Ji , Jie Yan , Honggen Peng . Modulation of dinuclear site by orbital coupling to boost catalytic performance. Chinese Journal of Structural Chemistry, 2024, 43(8): 100360-100360. doi: 10.1016/j.cjsc.2024.100360
10. [10]
  Zhibin Ren , Shan Li , Xiaoying Liu , Guanghao Lv , Lei Chen , Jingli Wang , Xingyi Li , Jiaqing Wang . Penetrating efficiency of supramolecular hydrogel eye drops: Electrostatic interaction surpasses ligand-receptor interaction. Chinese Chemical Letters, 2024, 35(11): 109629-. doi: 10.1016/j.cclet.2024.109629
11. [11]
  Cheng Wang , Ji Wang , Dong Liu , Zhi-Ling Zhang . Advances in virus-host interaction research based on microfluidic platforms. Chinese Chemical Letters, 2024, 35(12): 110302-. doi: 10.1016/j.cclet.2024.110302
12. [12]
  Weihong Ding , Kaiyue Song , Xianglong Li , Xiaoxia Sun . High-temperature-stable RRAMs with well-defined thermal effect mechanisms enable by engineering of robust 2D <100>-oriented organic-inorganic hybrid perovskites. Chinese Chemical Letters, 2025, 36(4): 110495-. doi: 10.1016/j.cclet.2024.110495
13. [13]
  Bin Chen , Chaoyang Zheng , Dehuan Shi , Yi Huang , Renxia Deng , Yang Wei , Zheyuan Liu , Yan Yu , Shenghong Zhong . p-d orbital hybridization induced by CuGa2 promotes selective N2 electroreduction. Chinese Journal of Structural Chemistry, 2025, 44(1): 100468-100468. doi: 10.1016/j.cjsc.2024.100468
14. [14]
  Jinli Chen , Shouquan Feng , Tianqi Yu , Yongjin Zou , Huan Wen , Shibin Yin . Modulating Metal-Support Interaction Between Pt3Ni and Unsaturated WOx to Selectively Regulate the ORR Performance. Chinese Journal of Structural Chemistry, 2023, 42(10): 100168-100168. doi: 10.1016/j.cjsc.2023.100168
15. [15]
  Yan-Bo Li , Yi Li , Liang Yin . Copper(Ⅰ)-catalyzed diastereodivergent construction of vicinal P-chiral and C-chiral centers facilitated by dual "soft-soft" interaction. Chinese Chemical Letters, 2024, 35(7): 109294-. doi: 10.1016/j.cclet.2023.109294
16. [16]
  Fanxin Kong , Hongzhi Wang , Huimei Duan . Inhibition effect of sulfation on Pt/TiO2 catalysts in methane combustion. Chinese Journal of Structural Chemistry, 2024, 43(5): 100287-100287. doi: 10.1016/j.cjsc.2024.100287
17. [17]
  Min Fu , Pan He , Sen Zhou , Wenqiang Liu , Bo Ma , Shiying Shang , Yaohao Li , Ruihan Wang , Zhongping Tan . An unexpected stereochemical effect of thio-substituted Asp in native chemical ligation. Chinese Chemical Letters, 2024, 35(8): 109434-. doi: 10.1016/j.cclet.2023.109434
18. [18]
  Yixia Zhang , Caili Xue , Yunpeng Zhang , Qi Zhang , Kai Zhang , Yulin Liu , Zhaohui Shan , Wu Qiu , Gang Chen , Na Li , Hulin Zhang , Jiang Zhao , Da-Peng Yang . Cocktail effect of ionic patch driven by triboelectric nanogenerator for diabetic wound healing. Chinese Chemical Letters, 2024, 35(8): 109196-. doi: 10.1016/j.cclet.2023.109196
19. [19]
  Yuan Dong , Mutian Ma , Zhenyang Jiao , Sheng Han , Likun Xiong , Zhao Deng , Yang Peng . Effect of electrolyte cation-mediated mechanism on electrocatalytic carbon dioxide reduction. Chinese Chemical Letters, 2024, 35(7): 109049-. doi: 10.1016/j.cclet.2023.109049
20. [20]
  Botao Gao , He Qi , Hui Liu , Jun Chen . Role of polarization evolution in the hysteresis effect of Pb-based antiferroelecrtics. Chinese Chemical Letters, 2024, 35(4): 108598-. doi: 10.1016/j.cclet.2023.108598

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(697)
HTML views(2)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142