A Gaint Donor-Acceptor Molecular Switch Compound: Synthesis and Properties

doi:10.6023/A22060283

Abstract

A novel donor-acceptor (D-A) molecular switch compound (compound 1) in which porphyrin is the donor and fullerene is the acceptor was synthesized using a conformationally variable resorcin[4]arene cavitand as the molecular switch parent. As far as we know, this molecule is the largest D-A resorcin[4]arene cavitand (molecular weight: 3064.9966). In order to synthesize this D-A molecular switch, firstly, compounds 4 and 9 were synthesized by Sonogashira coupling and Suzuki coupling, respectively. Then, both compounds 4 and 9 react with compound 5 to obtain arm compounds 6 and 10. Considering the low yield in the process of synthesizing porphyrins, compound 6 was first reacted with resorcin[4]arene 11 to obtain compound 12. Undoubtedly, a by-product with two compound 6 arms simultaneously will be produced. So, compound 12 can be obtained in a higher yield by adding compound 6 in batches. Then compound 13 can be obtained by the Prato reaction, and finally, compound 1 can be obtained by reacting with porphyrin arm 10. The structure of 1 was thoroughly confirmed by ¹H NMR spectroscopy (nuclear magnetic resonance spectroscopy), ¹³C NMR spectroscopy, 2D (two-dimensional) NMR spectroscopy and HRMS (high-resolution mass spectrometry). Under pH induction, compound 1 can undergo a conformational change from the original contracted state (vase) to the expanded state (kite). However, the conformational change of 1 cannot be induced under the conditions of lowering the temperature and introducing Zn²⁺. The reason for the pH-induced conformational change may be that the addition of acid causes the protonation of the N atom on the quinoxaline arm, which makes the formed electrostatic repulsion push the arms away from each other. In addition, the photophysical properties of 1 were also studied. The photophysical processes were investigated with steady-state UV-visible absorption and transient fluorescence spectroscopies. Compound 1 shows efficient intramolecular singlet-singlet energy transfer from the porphyrin moiety to the fullerene moiety. The rate constants and eﬃciency of the singlet-singlet energy transfer are calculated at 1.1×10⁷ s^-1 and 9.63%, respectively.

Key words: molecular switch, donor-acceptor, porphyrin-fullerene, resorcin[4]arene cavitand, energy transfer

Cite this article

Yuguang Sui, Jinrong Zhou, Pan Liao, Wenjie Liang, Hai Xu. A Gaint Donor-Acceptor Molecular Switch Compound: Synthesis and Properties[J]. Acta Chimica Sinica, 2022, 80(8): 1061-1065.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 6

Figure 1. Resorcin[4]arene cavitands with differently functional arms

Scheme 1. The synthetic route to compound 1

Figure 2. 1H NMR of compound 1 at different pH (c=7.4×10-3 mol/L, solvent: CDCl3) at different pH (c=7.4×10-3 mol/L, solvent: CDCl3)

Figure 3. 1H NMR of compound 1 at different temperatures (c=8.2×10-3 mol/L, solvent: CD2Cl2)

Figure 4. UV-Vis absorption spectra of compounds 10, 13 and 1 (c=2.5×10-6 mol/L, solvent: toluene). Inset: partial magnification; (b) steady fluorescence emission spectra of compounds 10 and 1 (c=2.5×10-6 mol/L, λex=425 nm, solvent: toluene)

Figure 5. Fluorescence decay curves of compounds 10 and 1 at 665 nm (c=2.5×10-6 mol/L, λex=425 nm, solvent: toluene)

References 30

[1]	Kroto, H. W.; Heath, J. R.; O’Brien, S. C.; Curl, R. F.; Smalley, R. E. Nature 1985, 318, 162. doi: 10.1038/318162a0
[2]	Badgurjar, D.; Seetharaman, S.; D’Souza, F.; Chitta, R. Chem. Eur. J. 2021, 27, 2184. doi: 10.1002/chem.202004262
[3]	Krätschmer, W.; Lamb, L. D.; Fostiropoulos, K.; Huffman, D. R. Nature 1990, 347, 354. doi: 10.1038/347354a0
[4]	Guldi, D. M. Chem. Commun. 2000, 321.
[5]	Yu, X.; Wang, B.; Kim, Y.; Park, J.; Ghosh, S.; Dhara, B.; Mukhopadhyay, R. D.; Koo, J.; Kim, I.; Kim, S.; Hwang, I. C.; Seki, S.; Guldi, D. M.; Baik, M. H.; Kim, K. J. Am. Chem. Soc. 2020, 142, 12596. doi: 10.1021/jacs.0c05339
[6]	Zarrabi, N.; Poddutoori, P. K. Coord. Chem. Rev. 2021, 429, 213561. doi: 10.1016/j.ccr.2020.213561
[7]	Hölzel, H.; Haines, P.; Kaur, R.; Lungerich, D.; Jux, N.; Guldi, D. M. J. Am. Chem. Soc. 2022, 144, 8977. doi: 10.1021/jacs.2c00456
[8]	Zarrabi, N.; Agatemor, C.; Lim, G. N.; Matula, A. J.; Bayard, B. J.; Batista, V. S.; D’Souza, F.; Poddutoori, P. K. J. Phys. Chem. C 2019, 123, 131. doi: 10.1021/acs.jpcc.8b09500
[9]	Zarrabi, N.; Seetharaman, S.; Chaudhuri, S.; Holzer, N.; Batista, V. S.; van der Est, A.; D’Souza, F.; Poddutoori, P. K. J. Am. Chem. Soc. 2020, 142, 10008. doi: 10.1021/jacs.0c01574
[10]	Nikolaou, V.; Charisiadis, A.; Stangel, C.; Charalambidis, G.; Coutsolelos, A. G. J. Carbon Res. 2019, 5, 57.
[11]	Bottari, G.; Trukhina, O.; Ince, M.; Torres, T. Coord. Chem. Rev. 2012, 256, 2453. doi: 10.1016/j.ccr.2012.03.011
[12]	Moran, J. R.; Karbach, S.; Cram, D. J. J. Am. Chem. Soc. 1982, 104, 5826. doi: 10.1021/ja00385a064
[13]	Moran, J. R.; Ericson, J. L.; Dalcanale, E.; Bryant, J. A.; Knobler, C. B.; Cram, D. J. J. Am. Chem. Soc. 1991, 113, 5707. doi: 10.1021/ja00015a026
[14]	Cram, D. J.; Choi, H.; Bryant, J. A.; Knobler, C. B. J. Am. Chem. Soc. 1992, 114, 7748. doi: 10.1021/ja00046a022
[15]	Soncini, P.; Bonsignore, S.; Dalcanale, E.; Ugozzoli, F. J. Org. Chem. 1992, 57, 17. doi: 10.1021/jo00027a008
[16]	Skinner, P. J.; Cheetham, A. G.; Beeby, A.; Gramlich, V.; Diederich, F. Helv. Chim. Acta 2001, 84, 2146. doi: 10.1002/1522-2675(20010711)84:7【-逻辑与-】#x00026;lt;2146::AID-HLCA2146【-逻辑与-】#x00026;gt;3.0.CO;2-K
[17]	Azov, V. A.; Diederich, F.; Lill, Y.; Hecht, B. Helv. Chim. Acta 2003, 86, 2149. doi: 10.1002/hlca.200390172
[18]	Azov, V. A.; Jaun, B.; Diederich, F. Helv. Chim. Acta 2004, 87, 449. doi: 10.1002/hlca.200490043
[19]	Azov, V. A.; Schlegel, A.; Diederich, F. Angew. Chem. Int. Ed. 2005, 44, 4635. doi: 10.1002/anie.200500970
[20]	Azov, V. A.; Beeby, A.; Cacciarini, M.; Cheetham, A. G.; Diederich, F.; Frei, M.; Gimzewski, J. K.; Gramlich, V.; Hecht, B.; Jaun, B.; Latychevskaia, T.; Lieb, A.; Lill, Y.; Marotti, F.; Schlegel, A.; Schlitterler, R. R.; Skinner, P. J.; Seiler, P.; Yamakoshi, Y. Adv. Funct. Mater. 2006, 16, 147. doi: 10.1002/adfm.200500181
[21]	Frei, M.; Marotti, F.; Diederich, F. Chem. Commun. 2004, 1362.
[22]	Pochorovski, I.; Diederich, F. Acc. Chem. Res. 2014, 47, 2096. doi: 10.1021/ar500104k
[23]	Pochorovski, I.; Ebert, M. O.; Gisselbrecht, J. P.; Boudon, C.; Schweizer, W. B.; Diederich, F. J. Am. Chem. Soc. 2012, 134, 14702. doi: 10.1021/ja306473x pmid: 22906195
[24]	Pochorovski, I.; Knehans, T.; Nettels, D.; Müller, A. M.; Schweizer, W. B.; Caflisch, A.; Schuler, B.; Diederich, F. J. Am. Chem. Soc. 2014, 136, 2441. doi: 10.1021/ja4104292 pmid: 24490940
[25]	Xu, H.; Zhao, S.; Ren, Y.; Cai, J.; Wang, X.; Lin, Y. Chem. J. Chinese U. 2015, 36, 2421. (in Chinese)
	(徐海, 赵斯祺, 任扬, 蔡健峰, 汪翔, 林雨霖, 高等学校化学学报, 2015, 36, 2421.)
[26]	Liang, Y.; Tang, J.; Wang, X.; Zhao, S.; Luo, T.; Shuai, C.; Jiang, J.; Cai, J.; Xu, H. ChemistrySelect 2018, 3, 5361. doi: 10.1002/slct.201800931
[27]	Liang, Y.; Wang, X.; Zhao, S.; He, P.; Luo, T.; Jiang, J.; Liang, W.; Cai, J.; Xu, H. ChemistrySelect 2019, 4, 10316. doi: 10.1002/slct.201902680
[28]	Calderon-Cerquera, K.; Parra, A.; Madrid-Úsuga, D.; Cabrera- Espinoza, A.; Melo-Luna, C. A.; Reina, J. H.; Insuasty, B.; Ortiz, A. Dyes Pigments 2021, 184, 108752. doi: 10.1016/j.dyepig.2020.108752
[29]	Che, Y.; Yuan, X.; Sun, L.; Xu, H.; Zhao, X.; Cai, F.; Liu, L.; Zhao, J. J. Mater. Chem. C 2020, 8, 15839. doi: 10.1039/D0TC03490H
[30]	Fu, B.; Che, Y.; Yuan, X.; Sun, L.; Xu, H.; Zhao, J.; Liu, L. Dyes Pigments 2021, 196, 109754. doi: 10.1016/j.dyepig.2021.109754

巨型给-受体分子开关化合物的合成及性质研究