路易斯酸碱对在材料化学应用中的研究进展

doi:10.6023/cjoc202301009

摘要/Abstract

由于路易斯酸碱对(Lewis Pairs, LPs)合成的多样性以及便于调整的空间位阻和电子效应, 它们在小分子活化(例如CO₂, H₂, CO, SO₂, N₂O)和不对称催化等领域得到了快速发展. 新型功能高分子材料的合成一直是材料化学的研究热点, 将路易斯酸(LAs)和路易斯碱(LBs)引入到聚合物骨架中, 能够赋予材料独特的性能, 极大地丰富了功能高分子材料的种类. 综述了近年来大分子LAs和LBs的合成及研究进展, 阐明了LPs和路易斯酸碱对聚合(LPP)在材料化学应用中的多样性和多功能性. 重点介绍了LPs在构筑超分子聚合物网络, CO₂捕获和释放以及新型拓扑聚合物合成上的应用, 并提出该领域存在的挑战以及未来的发展方向.

关键词: 路易斯酸碱对, 路易斯酸碱对聚合, 超分子聚合物网络, CO₂捕获和释放, 聚合物拓扑结构

Lewis Pairs (LPs) have made a rapid development in the fields of small molecule activation (such as CO₂, H₂, CO, SO₂, N₂O) and asymmetric catalysis, mainly thanks to the diversity of Lewis Pairs (LPs) synthesis and the convenient tunability of steric hindrance and electronic effects. The synthesis of novel functional polymer materials has always been a research hotspot in material chemistry. The introduction of Lewis acids (LAs) and Lewis bases (LBs) into the polymer skeleton can endow materials with unique properties and greatly enrich the types of functional polymer materials. Herein, this review summarizes the recent advance and synthesis of macro-LAs and macro-LBs, but also illustrates the diversity and versatility of LPs and Lewis pair polymerizations (LPPs) in the application of material chemistry. This review highlights the construction of supramolecular polymer networks, CO₂ capture and release, and the synthesis of novel topological polymers. In addition, the challenges and the future development trend in this field are also proposed.

Key words: Lewis pairs, Lewis pair polymerization, supramolecular polymer networks, CO₂ capture and release, topological polymer

引用此文

肖丽娟, 张艳平, 洪缪. 路易斯酸碱对在材料化学应用中的研究进展[J]. 有机化学, 2023, 43(3): 949-960.

Lijuan Xiao, Yanping Zhang, Miao Hong. Research Progress of Lewis Acid and Base Pairs Applied in Materials Chemistry[J]. Chinese Journal of Organic Chemistry, 2023, 43(3): 949-960.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 14

图式1. (A)经典的路易斯酸碱加合物(CLA)、松散的路易斯酸碱对(ILP)和受阻路易斯酸碱对(FLP), 以及(B)路易斯酸碱对聚合中的链引发和链增长

Scheme 1. (A) Classical Lewis adduct (CLA), interacting Lewis pair (ILP) and frustrated Lewis pair (FLP), and (B) chain initiation and propagation in LPP

图式2. (A)基于有机硅-硼酸盐与氨基硅酮动态相互作用的可逆交联, 以及(B)二-2-噻吩基硼基取代聚苯乙烯和含吡啶基遥爪聚合物PDMS之间的热可逆交联

Scheme 2. (A) Reversible cross-linking based on dynamic interaction of the LP between silicone-boronate and aminosilicones, and (B) thermally reversible crosslinking between di-2-thienylboryl-substituted PS and pyridine-bearing telechelic PDMS

图式3. LA功能化聚苯乙烯与LB功能化PDMS的合成及其瞬态聚合物网络形成

Scheme 3. Synthesis of LA functionalized polystyrene and LB functionalized PDMS and the formation of transient polymer networks

图式4. 膦LB和硼烷LA功能化的聚苯乙烯形成聚合物FLP和添加DEAD交联剂构建聚合物网络凝胶

Scheme 4. Polymeric FLP based on phosphorous LB- and borane LA-functionalized polystyrene and the formation of a network gel by addition of cross-linking agent DEAD

图式5. 环氧化合物触发PSt-P和PSt-B形成聚(FLP)交联网络示意图

Scheme 5. Preparation of a poly (FLP) crosslinking network by cycloether PSt-P and PSt-B

图式6. 基于聚合物FLP (P1和P2)的第二代CO2响应系统

Scheme 6. Second-generation CO2-responsive system based on polymer-FLP (P1 and P2) Second-generation CO2-responsive system based on polymer-FLP (P1 and P2)

图式7. 三叶状受阻路易斯酸碱对形成CO2动态交联的聚合物网络

Scheme 7. Formation of dynamic CO2-cross-linked polymer networks based on trefoil-like frustrated Lewis pair

图式8. poly(NHC)的合成以及poly(NHC)催化胺与CO2的制备甲酰胺

Scheme 8. Synthesis of poly(NHC) and poly(NHC)-catalyzed CO2 reduction to formamid with amine

图式9. (A) poly(NHC)的合成及CO2捕获过程, 以及(B)聚咪唑盐离子液体和poly(NHC)-CO2加合物的制备

Scheme 9. (A) Synthesis of poly(NHC) and the subsequent capture of CO2, and (B) synthesis of polyimidazole salt ionic liquid and the preparation of poly(NHC)-CO2 adduct (A) Synthesis of poly(NHC) and the subsequent capture of CO2, and (B) synthesis of polyimidazole salt ionic liquid and the preparation of poly(NHC)-CO2 adduct

图式10. (A) poly(RNHC) (R=iPr, nBu)的合成以及(B) poly(RNHC)与C60形成的路易斯酸碱加合物

Scheme 10. (A) Synthetic route to poly(RNHC) (R=iPr, nBu), and (B) polymeric Lewis adducts between the poly(N-heterocyclic carbene) [poly(NHC)] and C60

图式11. (A) P3HT-(CH2)3-MIM和P3HT-(CH2)3-VIM的合成, (B) P3HT-(CH2)3-MIM与C60形成的加合物, 以及(C)刷状聚合物P[P3HT-(CH2)3-VIM-C60]的合成

Scheme 11. (A) Synthetic routes of P3HT-(CH2)3-MIM and P3HT-(CH2)3-VIM, (B) linked D-A adduct of P3HT-(CH2)3-MIM-C60, and (C) the polymer brush of P[P3HT-(CH2)3-VIM-C60]

图式12. LP介导的两种表面引发聚合(SIP)制备线性聚合物刷和瓶刷聚合物

Scheme 12. Preparation of linear polymer brushes and bottle-brush brushes via LPP using SIP-initiating systems (A) the combination of self-assembled monolayers (SAMs) with NHO ends, (B) surface-attached macroinitiators bearing NHOs

图式13. poly(NHO)的合成及P(δ-VL)和PMMA侧链分子刷的合成示意图

Scheme 13. Synthesis of poly(NHO) and schematic diagram of molecular brush with side chain of P(δ-VL) and PMMA, respectively

图式14. iBu2Al(BHT)/NHO一锅一步法制备PISA策略示意图

Scheme 14. Preparation of PISA catalyzed by iBu2Al(BHT)/NHO via a one-pot reaction

参考文献 68

[1]	Lewis, G. N. Valence and the Structure of Atoms and Molecules, Chemical Catalog Co., New York, 1923.
[2]	Welch, G. C.; Juan, R. R. S.; Masuda, J. D.; Stephan, D. W. Science 2006, 314, 1124. doi: 10.1126/science.1134230
[3]	Stephan, D. W. Acc. Chem. Res. 2015, 48, 306. doi: 10.1021/ar500375j
[4]	Stephan, D. W.; Erker, G. Angew. Chem., Int. Ed. 2015, 54, 6400. doi: 10.1002/anie.201409800
[5]	Scott, D. J.; Fuchter, M. J.; Ashley, A. E. Chem. Soc. Rev. 2017, 46, 5689. doi: 10.1039/C7CS00154A
[6]	Meng, W.; Feng, X.; Du, H. Acc. Chem. Res. 2018, 51, 191. doi: 10.1021/acs.accounts.7b00530
[7]	Hong, M.; Chen, J.; Chen, E. Y. X. Chem. Rev. 2018, 118, 10551. doi: 10.1021/acs.chemrev.8b00352
[8]	McGraw, M. L.; Chen, E. Y. X. Macromolecules 2020, 53, 6102. doi: 10.1021/acs.macromol.0c01156
[9]	Zhang, Y.; Miyake, G. M.; John, M. G.; Falivene, L.; Caporaso, L.; Cavallo, L.; Chen, E. Y. X. Dalton Trans. 2012, 41, 9119. doi: 10.1039/c2dt30427a
[10]	Jia, Y.-B.; Wang, Y.-B.; Ren, W.-M.; Xu, T.; Wang, J.; Lu, X.-B. Macromolecules 2014, 47, 1966. doi: 10.1021/ma500047d
[11]	McGraw, M. L.; Clarke, R. W.; Chen, E. Y. X. J. Am. Chem. Soc. 2020, 142, 5969. doi: 10.1021/jacs.0c01127
[12]	Wang, H.; Wang, Q.; He, J.; Zhang, Y. Polym. Chem. 2019, 10, 3597. doi: 10.1039/C9PY00427K
[13]	Zhang, Y.; Miyake, G. M.; Chen, E. Y. X. Angew. Chem., Int. Ed. 2010, 49, 10158. doi: 10.1002/anie.201005534
[14]	Wang, X.-J.; Hong, M. Angew. Chem., Int. Ed. 2020, 59, 2664. doi: 10.1002/anie.v59.7
[15]	Song, Y.; He, J.; Zhang, Y.; Gilsdorf, R. A.; Chen, E. Y. X. Nat. Chem. 2022, 15, 366. doi: 10.1038/s41557-022-01097-7
[16]	Zhao, W.; He, J.; Zhang, Y. Sci. Bull. 2019, 64, 1830. doi: 10.1016/j.scib.2019.08.025
[17]	Bai, Y.; Zhang, Y. Acta Polym. Sin. 2019, 50, 233. (in Chinese)
	(白云, 张越涛, 高分子学报, 2019, 50, 233.)
[18]	Xu, T.; Li, C. Prog. Chem. 2015, 27, 1087. (in Chinese)
	(徐铁齐, 李长宏, 化学进展, 2015, 27, 1087.) doi: 10.7536/PC150166
[19]	Xu, T.; Chen, E. Y. X. J. Am. Chem. Soc. 2014, 136, 1774. doi: 10.1021/ja412445n
[20]	Guan, Y.; Chang, K.; Sun, Q.; Xu, X. Chin. J. Org. Chem. 2022, 42, 1326. (in Chinese) doi: 10.6023/cjoc202112008
	(管怡雯, 常克俭, 孙千林, 徐信, 有机化学, 2022, 42, 1326.) doi: 10.6023/cjoc202112008
[21]	Wang, B.; Ji, H.; Li, Y. Acta Polym. Sin. 2020, 51, 1104. (in Chinese)
	(王彬, 季鹤源, 李悦生, 高分子学报, 2020, 51, 1104.)
[22]	Jia, Y.-G.; Jin, J.; Liu, S.; Ren, L.; Luo, J.; Zhu, X. X. Biomacromolecules 2018, 19, 626. doi: 10.1021/acs.biomac.7b01707
[23]	Yang, Y.; Urban, M. W. Adv. Mater. Interfaces 2018, 5, 1800384. doi: 10.1002/admi.v5.17
[24]	Yan, X.; Wang, F.; Zheng, B.; Huang, F. Chem. Soc. Rev. 2012, 41, 6042. doi: 10.1039/c2cs35091b
[25]	Cordier, P.; Tournilhac, F.; Soulié-Ziakovic, C.; Leibler, L. Nature 2008, 451, 977. doi: 10.1038/nature06669
[26]	Li, C.-H.; Zuo, J.-L. Adv. Mater. 2020, 32, 1903762.
[27]	Burattini, S.; Greenland, B. W.; Merino, D. H.; Weng, W.; Seppala, J.; Colquhoun, H. M.; Hayes, W.; Mackay, M. E.; Hamley, I. W.; Rowan, S. J. J. Am. Chem. Soc. 2010, 132, 12051. doi: 10.1021/ja104446r pmid: 20698543
[28]	Nakahata, M.; Takashima, Y.; Yamaguchi, H.; Harada, A. Nat. Commun. 2011, 2, 511. doi: 10.1038/ncomms1521 pmid: 22027591
[29]	Urban, M. W.; Davydovich, D.; Yang, Y.; Demir, T.; Zhang, Y.; Casabianca, L. Science 2018, 362, 220. doi: 10.1126/science.aat2975
[30]	Yolsal, U.; Horton, T. A. R.; Wang, M.; Shaver, M. P. Prog. Polym. Sci. 2020, 111, 101313. doi: 10.1016/j.progpolymsci.2020.101313
[31]	Hou, Q.; Liu, L.; Mellerup, S. K.; Wang, N.; Peng, T.; Chen, P.; Wang, S. Org. Lett. 2018, 20, 6467. doi: 10.1021/acs.orglett.8b02774
[32]	Mellerup, S. K.; Wang, S. Chem. Soc. Rev. 2019, 48, 3537. doi: 10.1039/c9cs00153k pmid: 31070642
[33]	Kristensen, T. E.; Hansen, T. Eur. J. Org. Chem. 2010, 2010, 3179.
[34]	Wang, M.; Nudelman, F.; Matthes, R. R.; Shaver, M. P. J. Am. Chem. Soc. 2017, 139, 14232. doi: 10.1021/jacs.7b07725
[35]	Dodge, L.; Chen, Y.; Brook, M. A. Chemistry 2014, 20, 9349.
[36]	Vidal, F.; Lin, H.; Morales, C.; Jäkle, F. Molecules 2018, 23, 405. doi: 10.3390/molecules23020405
[37]	Vidal, F.; Gomezcoello, J.; Lalancette, R. A.; Jäkle, F. J. Am. Chem. Soc. 2019, 141, 15963. doi: 10.1021/jacs.9b07452
[38]	Yolsal, U.; Horton, T. A. R.; Wang, M.; Shaver, M. P. J. Am. Chem. Soc. 2021, 143, 12980. doi: 10.1021/jacs.1c06408 pmid: 34387464
[39]	Birkmann, B.; Voss, T.; Geier, S. J.; Ullrich, M.; Kehr, G.; Erker, G.; Stephan, D. W. Organometallics 2010, 29, 5310. doi: 10.1021/om1003896
[40]	Chen, L.; Liu, R.; Yan, Q. Angew. Chem., Int. Ed. 2018, 57, 9336. doi: 10.1002/anie.201804034
[41]	Chen, L.; Liu, R.; Hao, X.; Yan, Q. Angew. Chem., Int. Ed. 2019, 58, 264. doi: 10.1002/anie.201812365
[42]	Stephan, D. W. Science 2016, 354, aaf7229.
[43]	Smith, C. A.; Narouz, M. R.; Lummis, P. A.; Singh, I.; Nazemi, A.; Li, C.-H.; Crudden, C. M. Chem. Rev. 2019, 119, 4986. doi: 10.1021/acs.chemrev.8b00514
[44]	Van Ausdall, B. R.; Glass, J. L.; Wiggins, K. M.; Aarif, A. M.; Louie, J. J. Org. Chem. 2009, 74, 7935. doi: 10.1021/jo901791k pmid: 19775141
[45]	Grossmann, A.; Enders, D. Angew. Chem., Int. Ed. 2012, 51, 314. doi: 10.1002/anie.201105415 pmid: 22121084
[46]	Holschumacher, D.; Bannenberg, T.; Hrib, C. G.; Jones, P. G.; Tamm, M. Angew. Chem., Int. Ed. 2008, 47, 7428. doi: 10.1002/anie.200802705 pmid: 18666192
[47]	Huang, K.; Zhang, J.-Y.; Liu, F.; Dai, S. ACS Catal. 2018, 8, 9079. doi: 10.1021/acscatal.8b02151
[48]	Zhang, Y.; Zhao, L.; Patra, P. K.; Hu, D.; Ying, J. Y. Nano Today 2009, 4, 13. doi: 10.1016/j.nantod.2008.10.015
[49]	Tan, M.; Zhang, Y.; Ying, J. Y. Adv. Synth. Catal. 2009, 351, 1390. doi: 10.1002/adsc.v351:9
[50]	Riduan, S. N.; Ying, J. Y.; Zhang, Y. J. Catal. 2016, 343, 46. doi: 10.1016/j.jcat.2015.09.009
[51]	Zhou, H.; Zhang, W.-Z.; Wang, Y.-M.; Qu, J.-P.; Lu, X.-B. Macromolecules 2009, 42, 5419. doi: 10.1021/ma901109j
[52]	Pinaud, J.; Vignolle, J.; Gnanou, Y.; Taton, D. Macromolecules 2011, 44, 1900. doi: 10.1021/ma1024285
[53]	Coupillaud, P.; Pinaud, J.; Guidolin, N.; Vignolle, J.; Fèvre, M.; Veaudecrenne, E.; Mecerreyes, D.; Taton, D. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4530. doi: 10.1002/pola.26869
[54]	Coupillaud, P.; Vignolle, J.; Mecerreyes, D.; Taton, D. Polymer 2014, 55, 3404. doi: 10.1016/j.polymer.2014.02.043
[55]	Hong, M.; Chen, E. Y.-X. Polym. Chem. 2015, 6, 1741. doi: 10.1039/C4PY01488J
[56]	Wang, Y.; Hong, M.; Bailey, T. S.; Chen, E. Y.-X. Molecules 2017, 22, 1564. doi: 10.3390/molecules22091564
[57]	Li, Z.; Tang, M.; Liang, S.; Zhang, M.; Biesold, G. M.; He, Y.; Hao, S.-M.; Choi, W.; Liu, Y.; Peng, J.; Lin, Z. Prog. Polym. Sci. 2021, 116, 101387. doi: 10.1016/j.progpolymsci.2021.101387
[58]	Verduzco, R.; Li, X.; Pesek, S. L.; Stein, G. E. Chem. Soc. Rev. 2015, 44, 2405. doi: 10.1039/c4cs00329b pmid: 25688538
[59]	Feng, C.; Li, Y.; Yang, D.; Hu, J.; Zhang, X.; Huang, X. Chem. Soc. Rev. 2011, 40, 1282. doi: 10.1039/B921358A
[60]	Pelras, T.; Mahon, C. S.; Müllner, M. Angew. Chem., Int. Ed. 2018, 57, 6982. doi: 10.1002/anie.v57.24
[61]	Xie, G.; Martinez, M. R.; Olszewski, M.; Sheiko, S. S.; Matyjaszewski, K. Biomacromolecules 2019, 20, 27. doi: 10.1021/acs.biomac.8b01171
[62]	Wang, Y.; Hong, M.; Bailey, T. S.; Chen, E. Y. X. Molecules 2017, 22, 1564. doi: 10.3390/molecules22091564
[63]	Wang, Q.; Zhao, W.; Zhang, S.; He, J.; Zhang, Y.; Chen, E. Y. X. ACS Catal. 2018, 8, 3571. doi: 10.1021/acscatal.8b00333
[64]	Bai, Y.; He, J.; Zhang, Y. Angew. Chem., Int. Ed. 2018, 57, 17230. doi: 10.1002/anie.v57.52
[65]	Wang, Q.; Zhao, W.; He, J.; Zhang, Y.; Chen, E. Y.-X. Macromolecules 2017, 50, 123. doi: 10.1021/acs.macromol.6b02398
[66]	Hou, L.; Liang, Y.; Wang, Q.; Zhang, Y.; Dong, D.; Zhang, N. ACS Macro Lett. 2018, 7, 65. doi: 10.1021/acsmacrolett.7b00903
[67]	Chen, S.; Hou, L.; Wang, Q.; Dong, D.; Zhang, N. Polym. Chem. 2018, 9, 5470. doi: 10.1039/C8PY01257A
[68]	Li, C.; Zhao, W.; He, J.; Zhang, Y.; Zhang, W. Angew. Chem., Int. Ed. 2022, 61, e202202448.