基于分子间卤键的超分子平面大环自组装

doi:10.6023/A22080368

摘要/Abstract

本工作报道了含卤键供体和受体片段的三种芳酰胺分子(化合物1~3)的设计和合成, 并对固相中卤键的不同作用模式进行了探索和分析. 化合物1的晶体数据显示, 由于没有分子内氢键, 组成分子的三个芳环相互扭转一定角度, 并且在分子间交替排列的N···I和O···I卤键的控制下, 组装成了一条线型的超分子组装体. 由于酰胺羰基和两个紧邻的氟原子之间的排斥作用, 化合物2未能形成分子内三中心氢键. 在此基础上, 将三氟碘代苯作为卤键供体片段引入到化合物3中, 并且在折叠体骨架中嵌入了嘧啶单元. 化合物3的晶体数据显示, 基于多组有效的分子内三中心氢键和分子间较强的卤键作用, 双分子间形成了[1+1]的超分子大环. 另外, 由于嘧啶环的引入, 使得该超分子大环接近共平面.

关键词: 卤键, 氢键, 晶体工程, 超分子作用, 双分子大环

The design and synthesis of three kinds of arylamide molecules (compounds 1~3) containing halogen bonding donor and acceptor fragments, and the exploration and analyzation of different action modes of halogen bonding in solid phase were reported. Compounds 1 and 2 contain two tetrafluoroiodobenzene fragments, and compound 1 also contains a halogen receptor fragment—pyridine group. Isobutyl groups are introduced into the molecule to increase its solubility and crystallinity. And a pyrimidine fragment was introduced into compound 3, which has more aromatic rings. The two N atoms of the pyrimidine fragment can theoretically form intramolecular hydrogen bonds with the adjacent amide hydrogen atoms (—C(=O)NH), so that the whole molecule has the properties of hydrogen-bonded arylamide foldamer. Moreover, trifluorobenzene fragments were selected in compound 3 to eliminate the repulsion between excess fluorine atoms and carbonyls. The crystal structures reveal that the three aromatic rings in compound 1 are twisted with each other for there is no intramolecular hydrogen bond, and a supramolecular DNA-like double helix was assembled controlled by intermolecular N···I and O···I halogen bonds arranged alternately. Compound 2 failed to form an intramolecular three-center hydrogen bonding due to the repulsion between the amide carbonyl groups and the two fluorine atoms in close proximity. As expected, in the solid phase of compound 3, an effective three-center hydrogen bond is formed between the terminal trifluoroiodobenzene and the benzene ring attached to it. Moreover, the two N—H bonds connected to the pyrimidine ring also form two effective three-center hydrogen bonds. The difference is that the participants of these two groups of three-center hydrogen bonds include two N atoms in the pyrimidine ring. The four aromatic rings in compound 3 are nearly coplanar driven by these intramolecular three-center hydrogen bonds. Two sets of strong intermolecular (pyridine ring) N···I halogen bonds control the formation of [1+1] bimolecular supramolecular macrocycles with inner diameters of 1.36 nm and 1.07 nm in length and width. Moreover, the supramolecular macrocycle is near-planar due to the introduction of pyrimidine ring.

Key words: halogen bond, hydrogen bond, crystal engineering, supramolecular interaction, bimolecular macrocycle

引用此文

刘传志, 李芬, 王静静, 赵晓璐, 张婷美, 黄鑫, 邬梦丽, 户志远, 刘新明, 黎占亭. 基于分子间卤键的超分子平面大环自组装[J]. 化学学报, 2022, 80(10): 1365-1368.

Chuanzhi Liu, Fen Li, Jingjing Wang, Xiaolu Zhao, Tingmei Zhang, Xin Huang, Mengli Wu, Zhiyuan Hu, Xinming Liu, Zhanting Li. Self-assembly of Supramolecular Planar Macrocycle Driven by Intermolecular Halogen Bonding[J]. Acta Chimica Sinica, 2022, 80(10): 1365-1368.

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

分享此文

图/表 5

图1. 化合物 1~4的结构

Figure 1. The structures of compounds 1~4

图2. (a) N···I和O···I卤键诱导的双螺旋晶体结构(CCDC No. 2172319), 通过缓慢挥发二氯甲烷、甲醇和正己烷的混合溶剂(V/V/V=5:1:1)得到化合物1的单晶. (b) 双螺旋结构进一步组装之后的阵列图(淡紫色球代表碘原子, 淡蓝色球代表氮原子). (c) 双螺旋结构进一步组装之后的阵列侧视图. 为了清晰起见, 省略了H原子

Figure 2. (a) The double helices crystal structure controlled by the N···I and O···I halogen bonding (CCDC No. 2172319). Single crystals were grown by evaporation of the solution in CH2Cl2, methanol and n-hexane (V/V/V=5:1:1). (b) Arrays after further assembly of the double helices (light purple balls represents iodine atoms, light blue balls represents N atoms). (c) Side view of the array after further assembly of the double helices. H atoms were omitted for clarity

图3. (a) 化合物2的晶体结构(CCDC No. 2172322). 通过缓慢挥发二氯甲烷和正己烷(V/V=5:1)溶液得到单晶. (b) 分子间通过O···H氢键以近反平行的方式堆叠, 形成“三明治”状的堆积结构

Figure 3. (a) The crystal structure of compound 2 (CCDC No. 2172322). Single crystals were grown by evaporation of the solution in CH2Cl2 and n-hexane (V/V=5:1). (b) The molecules are stacked in opposite directions at a near-coplanar angle through intermolecular O···H hydrogen bonds, forming a sandwich-like structure

图4. 化合物3的双分子大环的晶体结构(CCDC No. 1903692). 缓慢挥发二氯甲烷、甲醇和二甲基亚砜(V/V/V=5:1:0.05)的混合溶液得到单晶

Figure 4. The crystal structure of dimeric supramolecular macrocycle from compound 3 (CCDC No. 1903692). Single crystals were grown by evaporation of the solution in CH2Cl2, methanol and dimethylsulfoxide (V/V/V=5:1:0.05)

图5. (a) 分属于两个不同大环的折叠体分子的分子间堆积模式. (b) 三环并列超分子阵列. (c) 三环并列超分子阵列的侧视图. 为了清晰起见, 省略了H原子

Figure 5. (a) Intermolecular stacking patterns of the foldamer molecules located on the interior of the two independent macrocycles. (b) The three-ring juxtaposed supramolecular array. (c) The side view of the three-ring juxtaposed supramolecular array. H atoms were omitted for clarity

参考文献 51

[1]	Politzer, P.; Lane, P.; Concha, M. C.; Ma, Y.; Murray, J. S. J. Mol. Model. 2007, 13, 305. pmid: 17013631
[2]	Rissanen, K. CrystEngComm 2008, 10, 1107. doi: 10.1039/b803329n
[3]	Priimagi, A.; Cavallo, G.; Metrangolo, P.; Resnati, G. Acc. Chem. Res. 2013, 46, 2686. doi: 10.1021/ar400103r
[4]	Mukherjee, A.; Tothadi, S.; Desiraju, G. R. Acc. Chem. Res. 2014, 47, 2514. doi: 10.1021/ar5001555
[5]	Cavallo, G.; Metrangolo, P.; Milani, R.; Pilati, T.; Priimagi, A.; Resnati, G.; Terraneo, G. Chem. Rev. 2016, 116, 2478. doi: 10.1021/acs.chemrev.5b00484
[6]	Fu, Y.; Xiang, Z.; Zhou, J.; Wu, X.; Li, Y.; Jiao, Y. Acta Chim. Sinica 2012, 70, 1847 ( in chinese). doi: 10.6023/A12060299
	(付昱, 向子龙, 周军, 吴欣蔚, 李妍, 焦永华, 化学学报, 2012, 70, 1847.)
[7]	Liu, C.-Z.; Wang, H.; Zhang, D.-W.; Zhao, X.; Li, Z.-T. Chin. J. Org. Chem. 2019, 39, 28. (in Chinese) doi: 10.6023/cjoc201812026
	(刘传志, 王辉, 张丹维, 赵新, 黎占亭, 有机化学, 2019, 39, 28.) doi: 10.6023/cjoc201812026
[8]	Ding, X.-H.; Chang, Y.-Z.; Ou, C.-Q.; Lin, J.-Y.; Xie, L.-H.; Huang, W. Natl. Sci. Rev. 2020, 7, 1906. doi: 10.1093/nsr/nwaa170
[9]	Gilday, L. C.; Robinson, S. W.; Barendt, T. A.; Langton, M. J.; Mullaney, B. R.; Beer, P. D. Chem. Rev. 2015, 115, 7118. doi: 10.1021/cr500674c pmid: 26165273
[10]	Kianimehra, A.; Akhbaria, K.; Whiteb, J.; Phuruangratc, A. Inorg. Chem. Commun. 2020, 115, 107864. doi: 10.1016/j.inoche.2020.107864
[11]	Bulfield, D.; Huber, S. M. Chem. Eur. J. 2016, 22, 14434. doi: 10.1002/chem.201601844
[12]	Sutar, R. L.; Huber, S. M. ACS Catal. 2019, 9, 9622. doi: 10.1021/acscatal.9b02894
[13]	Zhang, H.-M.; Toya, P. H. Adv. Synth. Catal. 2021, 363, 215. doi: 10.1002/adsc.202001019
[14]	Heinen, F.; Reinhard, D. L.; Engelage, E.; Huber, S. M. Angew. Chem. Int. Ed. 2021, 60, 5069. doi: 10.1002/anie.202013172
[15]	Ma, X.-K.; Zhang, W.; Liu, Z.; Zhang, H.; Zhang, B.; Liu, Y. Adv. Mater. 2021, 2007476.
[16]	Cao, J.; Yan, X.; He, W.; Li, X.; Li, Z.; Mo, Y.; Liu, M.; Jiang, Y.-B. J. Am. Chem. Soc. 2017, 139, 6605. doi: 10.1021/jacs.6b13171
[17]	Zheng, J.; Suwardi, A.; Wong, C. J. E.; Loh, X. J.; Li, Z. B. Nanoscale Adv. 2021, 3, 6342. doi: 10.1039/D1NA00485A
[18]	Gong, G.-F.; Lv, S.-H.; Han, J.-X.; Xie, F.; Li, Q.; Xia, N.; Zeng, W.; Chen, Y.; Wang, L.; Wang, J.-K.; Chen, S.-G. Angew. Chem. Int. Ed. 2021, 60, 14831. doi: 10.1002/anie.202102448
[19]	Borchers, T.-H.; Topić, F.; Christopherson, J. C.; Bushuyev, O.-S.; Vainauskas, J.; Titi, H. M.; Friščić, T.; Barrett, C. J. Nature Chem. 2022, 14, 574. doi: 10.1038/s41557-022-00909-0
[20]	Montaña, Á. M. ChemistrySelect 2017, 2, 9094. doi: 10.1002/slct.201701676
[21]	Sumii, Y.; Sasaki, K.; Tsuzuki, S.; Shibata, N. Molecules 2019, 24, 3610. doi: 10.3390/molecules24193610
[22]	Zhu, Z.; Wang, G.; Xu, Z.; Chen, Z.; Wang, J.; Shi, J.; Zhu, W. Phys. Chem. Chem. Phys. 2019, 21, 15106. doi: 10.1039/C9CP01379B
[23]	Zhao, H.; Sheng, S.; Hong, Y.; Zeng, H. J. Am. Chem. Soc. 2014, 136, 14270. doi: 10.1021/ja5077537
[24]	Jentzsch, A. V.; Matile, S. Top. Curr. Chem. 2014, 358, 205.
[25]	Huo, Y. P.; Zeng, H. Q. Acc. Chem. Res. 2016, 49, 922. doi: 10.1021/acs.accounts.6b00051
[26]	Shen, J.; Fan, J. R.; Ye, R. J.; Li, N.; Mu, Y. G.; Zeng, H. Q. Angew. Chem. Int. Ed. 2020, 59, 13328. doi: 10.1002/anie.202003512 pmid: 32346957
[27]	Zheng, S.-P.; Huang, L.-B.; Sun, Z.-H.; Barboiu, M. Angew. Chem. Int. Ed. 2021, 60, 566. doi: 10.1002/anie.201915287
[28]	Wang, C.-X.; Wang, S.-K.; Yang, H.-T.; Xiang, Y.-X.; Wang, X.-B.; Bao, C.-Y.; Zhu, L.-Y.; Tian, H.; Qu, D.-H. Angew. Chem. Int. Ed. 2021, 60, 14836. doi: 10.1002/anie.202102838
[29]	Chen, S.-J.; Wang, Y.-C.; Nie, T.; Bao, C.-Y.; Wang, C.-X.; Xu, T.-Y.; Lin, Q.-N.; Qu, D.-H.; Gong, X.-Q.; Yang, Y.; Zhu, L.-Y.; Tian, H. J. Am. Chem. Soc. 2018, 140, 17992. doi: 10.1021/jacs.8b09580
[30]	Pancholi, J.; Beer, P. D. Coord. Chem. Rev. 2020, 416, 213281. doi: 10.1016/j.ccr.2020.213281
[31]	Dong, S. Y.; Zheng, B.; Wang, F.; Huang, F. H. Acc. Chem. Res. 2014, 47, 1982. doi: 10.1021/ar5000456
[32]	Jungbauer, S. H.; Bulfield, D.; Kniep, F.; Lehmann, C. W.; Herdtweck, E.; Huber, S. M. J. Am. Chem. Soc. 2014, 136, 16740. doi: 10.1021/ja509705f pmid: 25406545
[33]	Gong, B. Chem.-Eur. J. 2001, 7, 4336. pmid: 11695666
[34]	Huc, I. Eur. J. Org. Chem. 2004, 17.
[35]	Li, Z.-T.; Hou, J.-L.; Li, C. Acc. Chem. Res. 2008, 41, 1343. doi: 10.1021/ar700219m
[36]	Roy, A.; Prabhakaran, P.; Baruah, P. K.; Sanjayan, G. J. Chem. Commun. 2011, 47, 11593. doi: 10.1039/c1cc13313f
[37]	Zhang, D.-W.; Zhao, X.; Hou, J.-L.; Li, Z.-T. Chem. Rev. 2012, 112, 5271. doi: 10.1021/cr300116k
[38]	Liu, C.-Z.; Yan, M.; Wang, H.; Zhang, D.-W.; Li, Z.-T. ACS Omega 2018, 3, 5165. doi: 10.1021/acsomega.8b00681
[39]	Sun, G.-J.; Nie, C.-B.; Zhao, X.; Li, Z.-T. Chin. J. Org. Chem. 2017, 37, 1757. (in Chinese) doi: 10.6023/cjoc201702012
	(孙广军, 聂承斌, 赵新, 黎占亭, 有机化学, 2017, 37, 1757.) doi: 10.6023/cjoc201702012
[40]	Yang, L.; Zhao, W.; Che, Y.-K.; Wang, Y.; Jiang, H. Chin. Chem. Lett. 2017, 28, 1659. doi: 10.1016/j.cclet.2017.06.006
[41]	Zhang, D.-W.; Wang, H.; Li, Z.-T. Macromol. Rapid Commun. 2017, 38, 1700179. doi: 10.1002/marc.201700179
[42]	Liu, C.-Z.; Koppireddi, S.; Wang, H.; Zhang, D.-W.; Li, Z.-T. Angew. Chem. Int. Ed. 2019, 58, 226. doi: 10.1002/anie.201811561
[43]	Liu, C.-Z.; Koppireddi, S.; Wang, H.; Zhang, D.-W.; Li, Z.-T. Chin. Chem. Lett. 2019, 30, 953. doi: 10.1016/j.cclet.2019.02.010
[44]	Koppireddi, S.; Liu, C.-Z.; Wang, H.; Zhang, D.-W.; Li, Z.-T. CrystEngComm 2019, 21, 2626. doi: 10.1039/c8ce02187b
[45]	Xu, Y.-Y.; Liu, C.-Z.; Wang, H.; Zhang, D.-W.; Li, Z.-T. Chin. J. Org. Chem. 2021, 41, 2848. (in Chinese) doi: 10.6023/cjoc202102012
	(许艳艳, 刘传志, 王辉, 张丹维, 黎占亭, 有机化学, 2021, 41, 2848.) doi: 10.6023/cjoc202102012
[46]	Yu, S.; Kalenius, E.; Frontera, A.; Rissanena, K. Chem. Commun. 2021, 57, 12464. doi: 10.1039/D1CC05616F
[47]	Metrangolo, P.; Meyer, F.; Pilati, T.; Resnati, G.; Terraneo, G. Angew. Chem. Int. Ed. 2008, 47, 6114. doi: 10.1002/anie.200800128
[48]	Gilday, L. C.; Robinson, S. W.; Barendt, T. A.; Langton, M. J.; Mullaney, B. R.; Beer, P. D. Chem. Rev. 2015, 115, 7118. doi: 10.1021/cr500674c pmid: 26165273
[49]	Wang, H.; Wang, W.; Jin, W.-J. Chem. Rev. 2016, 116, 5072. doi: 10.1021/acs.chemrev.5b00527 pmid: 26886515
[50]	Tepper, R.; Schubert, U. S. Angew. Chem. Int. Ed. 2018, 57, 6004. doi: 10.1002/anie.201707986 pmid: 29341377
[51]	Jiang, H.; Léger, J. M.; Huc, I. J. Am. Chem. Soc. 2003, 125, 3448. pmid: 12643704