Citation: Yishou WANG, Sha BAI, Yaoyu WANG, Yingfeng HAN. Controllable synthesis of polyimidazolium macrocycles based on metal-N-heterocyclic carbene templates[J]. Chinese Journal of Inorganic Chemistry, ;2024, 40(1): 221-231. doi: 10.11862/CJIC.20230378 shu

Controllable synthesis of polyimidazolium macrocycles based on metal-N-heterocyclic carbene templates

Yishou WANG ^{1, 2} ,
Sha BAI ^1,, ,
Yaoyu WANG ¹ ,
Yingfeng HAN ^1,,

1.
College of Chemistry and Materials Science, Northwest University, Xi'an 710127, China
2.
School of Chemical Engineering and Modern Materials, Shangluo University, Shangluo, Shaanxi 726000, China

Corresponding author: Sha BAI, baisha@nwu.edu.cn Yingfeng HAN, yfhan@nwu.edu.cn
Received Date: 12 October 2023
Revised Date: 15 December 2023

Figures(3)

In this investigation, we have devised a highly proficient methodology for synthesizing covalent organic macrocycles. The reaction involving bisimidazolium salts H₂-L1(BF₄)₂ (L1=A1, B1) with silver oxide resulted in the formation of binuclear silver metallacycles of the [Ag₂(L1)₂](BF₄)₂ (L1=A1, B1) classification. These metallacycles manifest olefinic appendages originating from two discrete dicarbene-bridged ligands arranged in pairs. Successive metal-carbene-templated ring-closing metathesis (RCM) precipitated the generation of two carbon-carbon double bonds connecting the two di-NHC ligands, thereby yielding cyclized binuclear silver metallacycles [Ag₂(L2)](BF₄)₂ (L2=A2, B2). Subsequent removal of the metal ions led to the formation of covalent organic macrocycles H₄-L2(BF₄)₄ (L2=A2, B2) with a substantial internal cavity. The dimensions and configuration of these polyimidazolium macrocycles can be facilely manipulated by adjusting the length and breadth of the bridging units in the ligands. Preliminary investigations indicate the potential applicability of this receptor in iodide sensing, detection, and recognition.
- template-directed synthesis,
- macrocycle,
- N-heterocyclic carbene,
- ring-closing metathesis
1. [1]
  Chen L, Chen Q H, Wu M Y, Jiang F L, Hong M C. Controllable coordination-driven self-assembly: from discrete metallocages to infinite cage-based frameworks[J]. Acc. Chem. Res., 2015,48(2):201-210. doi: 10.1021/ar5003076
2. [2]
  Pullen S, Clever G H. Mixed-ligand metal-organic frameworks and heteroleptic coordination cages as multifunctional scaffolds—A comparison[J]. Acc. Chem. Res., 2018,51(12):3052-3064. doi: 10.1021/acs.accounts.8b00415
3. [3]
  Zheng J, Lu Z, Wu K, Ning G H, Li D. Coinage-metal-based cyclic trinuclear complexes with metal-metal interactions: theories to experiments and structures to functions[J]. Chem. Rev., 2020,120(17):9675-9742. doi: 10.1021/acs.chemrev.0c00011
4. [4]
  TAO Y L, CHEN W C, WANG X L, SU Z M. Synthesis, crystal structures and fluorescence properties of two nanosized Zr-based molecular capsules[J]. Chinese J. Inorg. Chem., 2019,35(11):2108-2116. doi: 10.11862/CJIC.2019.224
5. [5]
  YU Y C, WANG H L, LI L L, HE C. Anthraquinone-based metal-organic cages as efficient photocatalysts for oxidation reactions[J]. Chinese J. Inorg. Chem., 2023,39(9):1649-1660.
6. [6]
  GUO T T, AN Y Y, ZHAO D, YAN J Z. Polyoxometalate-directing calix[4]resorcinarene-based giant[Co8] coordination cage: Self-assembly and electrochemical performance[J]. Chinese J. Inorg. Chem., 2023,39(9):1791-1799.
7. [7]
  Ward M D, Hunter C A, Williams N H. Coordination cages based on bis(pyrazolylpyridine) ligands: structures, dynamic behavior, guest binding, and catalysis[J]. Acc. Chem. Res., 2018,51(9):2073-2082. doi: 10.1021/acs.accounts.8b00261
8. [8]
  Jongkind L J, Caumes X, Hartendorp A P T, Reek J N H. Ligand template strategies for catalyst encapsulation[J]. Acc. Chem. Res., 2018,51(9):2115-2128. doi: 10.1021/acs.accounts.8b00345
9. [9]
  Fang Y, Powell J A, Li E, Wang Q, Perry Z, Kirchon A, Yang X Y, Xiao Z F, Zhu C F, Zhang L L, Huang F H, Zhou H C. Catalytic reactions within the cavity of coordination cages[J]. Chem. Soc. Rev., 2019,48(17):4707-4730. doi: 10.1039/C9CS00091G
10. [10]
  Sinha I, Mukherjee P S. Chemical transformations in confined space of coordination architectures[J]. Inorg. Chem., 2018,57(8):4205-4221. doi: 10.1021/acs.inorgchem.7b03067
11. [11]
  Roberts D A, Pilgrim B S, Nitschke J R. Covalent post-assembly modification in metallosupramolecular chemistry[J]. Chem. Soc. Rev., 2018,47(2):626-644. doi: 10.1039/C6CS00907G
12. [12]
  Levin E, Ivry E, Diesendruck C E, Lemcoff N G. Water in N-heterocyclic carbene-assisted catalysis[J]. Chem. Rev., 2015,115(11):4607-4692. doi: 10.1021/cr400640e
13. [13]
  Narayan S, Hahn F E. Metallosupramolecular architectures obtained from poly-N-heterocyclic carbene ligands[J]. Acc. Chem. Res., 2017,50(9):2167-2184. doi: 10.1021/acs.accounts.7b00158
14. [14]
  Zhong R, Lindhorst A C, Groche F J, Kühn F E. Immobilization of N-heterocyclic carbene compounds: A synthetic perspective[J]. Chem. Rev., 2017,117(3):1970-2058. doi: 10.1021/acs.chemrev.6b00631
15. [15]
  Lindhorst A C, Kaspar M, Altmann P J, Pöthig A, Kühn F E. Synthesis, characterization and derivatization of hydroxyl-functionalized iron(Ⅱ) bis(NHC) complexes[J]. Dalton Trans., 2018,47(6):1857-1867. doi: 10.1039/C7DT04774F
16. [16]
  Bai S, Han Y F. Metal-N-heterocyclic carbene chemistry directed toward metallosupramolecular synthesis and beyond[J]. Acc. Chem. Res., 2023,56(10):1213-1227. doi: 10.1021/acs.accounts.3c00102
17. [17]
  Zhang L, Das R, Li C T, Wang Y Y, Hahn F E, Hua K, Sun L Y, Han Y F. C₃-symmetric assemblies from trigonal polycarbene ligands and M^I ions for the synthesis of three-dimensional polyimidazolium cations[J]. Angew. Chem. Int. Ed., 2019,58(38):13360-13364. doi: 10.1002/anie.201907003
18. [18]
  Wang Y S, Li H, Bai S, Wang Y Y, Han Y F. N-Heterocyclic carbene-stabilized platinum nanoparticles within a porphyrinic nanocage for selective photooxidation[J]. Sci. China Chem., 2023,66(3):778-782.
19. [19]
  Wang Y S, Feng T, Wang Y Y, Hahn F E, Han Y F. Homo- and heteroligand poly-NHC metal assemblies: Synthesis by narcissistic and social self-sorting[J]. Angew. Chem. Int. Ed., 2018,57(48):15767-15771. doi: 10.1002/anie.201810010
20. [20]
  Wang Y S, Bai S, Wang Y Y, Han Y F. Process-tracing study on the post-assembly modification of poly-NHC-based metallosupramolecular cylinders with tunable aggregation-induced emission[J]. Chem. Commun., 2019,55(91):13689-13692. doi: 10.1039/C9CC07113J
21. [21]
  Wang Y S, Sun L Y, Wang Y Y, Han Y F. Phase-mediated controllable intramolecular and intermolecular photocycloadditions assisted by supramolecular templates[J]. Sci. China Chem., 2022,65(6):1129-1133. doi: 10.1007/s11426-022-1237-x
22. [22]
  WANG Z G, BIAN Q Q, HUANG B M, DENG Y, LIU S M. Synthesis, crystal structure and catalytic behavior of linear N-heterocyclic carbene silver[Ag(MEIm)₂]⁺[AgI₂]^- (MEIm=1-methyl-3-ethyl-imidazolyl)[J]. Chinese J. Inorg. Chem., 2012,28(1):191-194.
23. [23]
  LI X W, WANG X B, XU H J, YU X J, ZHUO S P. Synthesis, crystal structure and catalytic properties of ruthenium complexes bearing N-heterocyclic carbene ligand[J]. Chinese J. Inorg. Chem., 2014,30(6):1381-1387.
24. [24]
  YANG B B, ZHAO F, XU S X, HE H F. Syntheses and luminescent properties of green phosphorescent four-coordinated N-heterocyclic carbene copper(Ⅰ) complexes[J]. Chinese J. Inorg. Chem., 2019,35(6):1020-1026.
25. [25]
  Zhang Y F, Zhang Y W, Li Xin, Sun L Y, Han Y F. Synthesis of triarylborane-centered N-heterocyclic carbene cages with tunable photophysical properties[J]. Chem. Commun., 2023,59(16):2291-2294. doi: 10.1039/D2CC06584C
26. [26]
  Zhang Y F, Li X, Zhang H, Wang X Q, Sun L Y, Duan X L, Han Y F. Gold(Ⅰ) N-heterocyclic carbene complexes with tunable electronic properties for sensitive colorimetric detection of glutathione[J]. Mater. Chem. Front., 2023,7(14):2880-2888. doi: 10.1039/D3QM00167A
27. [27]
  Jin G F, Zhang Y Z, Yu L, Jiang W L, Li Y, Sun L Y, Li P, Han Y F. Radical organometallic nanocages with redox switchable poly-NHC ligands[J]. Nano Res., 2023,16(7):10678-10683. doi: 10.1007/s12274-023-5690-2
28. [28]
  Li M, Li Y, Li X, Wang F, Han Y F. An ultralong low-temperature phosphorescent pentagonal prismatic organometallic cylinder featuring pentaphenylpyrrole-N-heterocyclic carbenes[J]. Chin. J. Chem., 2023,41(12):1431-1436. doi: 10.1002/cjoc.202300026
29. [29]
  Wang C, Zhu Q W, Yu J G, Li X, Li H, Sun L Y, Han Y F. Hierarchical self-assembly of a radical naphthalenediimide-based N-heterocyclic carbene-Au(Ⅰ) macrocycle[J]. Inorg. Chem. Front., 2023,10(5):1457-1464. doi: 10.1039/D2QI02685F
30. [30]
  Zhang H, Li Y, Zhang Y F, Qiao X J, Sun L Y, Li J L, Wang Y Y, Han Y F. Solvato-controlled assembly and structural transformation of emissive poly-NHC-based organometallic cages and their applications in amino acid sensing and fluorescence imaging[J]. Chem.-Eur. J., 2023,29(23)e202300209. doi: 10.1002/chem.202300209
31. [31]
  Patil S A, Patil S A, Patil R. Medicinal applications of (benz)imidazole- and indole-based macrocycles[J]. Chem. Biol. Drug Des., 2017,89(4):639-649. doi: 10.1111/cbdd.12802
32. [32]
  Ermert P. Design, properties and recent application of macrocycles in medicinal chemistry[J]. Chimia, 2017,71(10):678-702. doi: 10.2533/chimia.2017.678
33. [33]
  Barlow T M A, Tourwé D, Ballet S. Cyclisation to form small, medium and large rings using catalyzed and uncatalysed azide-alkyne cycloadditions (AACs)[J]. Eur. J. Org. Chem., 2017,2017(32):4678-4694. doi: 10.1002/ejoc.201700521
34. [34]
  Ball M, Zhang B, Zhong Y, Fowler B, Xiao S, Ng F, Steigerwald M, Nuckolls C. Conjugated macrocycles in organic electronics[J]. Acc. Chem. Res., 2019,52(4):1068-1078. doi: 10.1021/acs.accounts.9b00017
35. [35]
  Mortensen K T, Osberger T J, King T A, Sore H F, Spring D R. Strategies for the diversity-oriented synthesis of macrocycles[J]. Chem. Rev., 2019,119(17):10288-10317. doi: 10.1021/acs.chemrev.9b00084
36. [36]
  Villemi D. Synthese de macrolides par methathese[J]. Tetrahedron Lett., 1980,21(18):1715-1718. doi: 10.1016/S0040-4039(00)77818-X
37. [37]
  Tsuji J, Hashiguchi S. Application of olefin metathesis to organic synthesis. Syntheses of civetone and macrolides[J]. Tetrahedron Lett., 1980,2(31):2955-2958.
38. [38]
  Altmann K H. The merger of natural product synthesis and medicinal chemistry: on the chemistry and chemical biology of epothilones[J]. Org. Biomol. Chem., 2004,2(15):2137-2152. doi: 10.1039/b405839a
39. [39]
  Zhang R Z, Liu Z Y. Recent progress in the synthesis of epothilones[J]. Curr. Org. Chem., 2004,8(4):267-290. doi: 10.2174/1385272043485927
40. [40]
  Nishioka T, Iwabuchi Y, Irie H, Hatakeyama S. Concise enantioselective synthesis of (+)-aspicilin based on a ruthenium catalyzed olefin metathesis reaction[J]. Tetrahedron Lett., 1980,39(31):5597-5600.
41. [41]
  Schrock R R, Czekelius C. Recent advances in the syntheses and applications of molybdenum and tungsten alkylidene and alkylidyne catalysts for the metathesis of alkenes and alkynes[J]. Adv. Synth. Catal., 2007,349(1/2):55-77.
42. [42]
  Vougloukalakis G J, Grubbs R H. Ruthenium-based heterocyclic carbene-coordinated olefin metathesis catalysts[J]. Chem. Rev., 2010,110(3):1746-1787. doi: 10.1021/cr9002424
43. [43]
  Bieniek M, Michrowska A, Usanov D L, Grela K. In an attempt to provide a user's guide to the galaxy of benzylidene, alkoxybenzylidene, and indenylidene ruthenium olefin metathesis catalysts[J]. Chem. Eur. J., 2008,14(3):806-818. doi: 10.1002/chem.200701340
44. [44]
  Conrad J C, Eelman M D, Silva J A D, Monfere S, Parnas H, Snelgrove J L, Fogg D E. Oligomers as intermediates in ring-closing metathesis[J]. J. Am. Chem. Soc., 2007,129(5):1024-1025. doi: 10.1021/ja067531t
45. [45]
  Hiraoka S, Yamauchi Y, Arakane R, Shionoya M. Template-directed synthesis of a covalent organic capsule based on a 3 nm-sized metallocapsule[J]. J. Am. Chem. Soc., 2009,131(33):11646-11647. doi: 10.1021/ja903324r
46. [46]
  Kim I, Ko K C, Lee W R, Cho J, Moon J H, Moon D, Sharma A, Lee J Y, Kim J S, Kim S. Calix[n]triazoles and related conformational studies[J]. Org. Lett., 2017,19(20):5509-5512. doi: 10.1021/acs.orglett.7b02557
47. [47]
  Beuerle F, Gole B. Covalent organic frameworks and cage compounds: Design and applications of polymeric and discrete organic scaffolds[J]. Angew. Chem. Int. Ed., 2018,57(18):4850-4878. doi: 10.1002/anie.201710190
1. [1]
  Yu Pang , Min Wang , Ning-Hua Yang , Min Xue , Yong Yang . One-pot synthesis of a giant twisted double-layer chiral macrocycle via [4 + 8] imine condensation and its X-ray structure. Chinese Chemical Letters, 2024, 35(10): 109575-. doi: 10.1016/j.cclet.2024.109575
2. [2]
  Huan Yao , Jian Qin , Yan-Fang Wang , Song-Meng Wang , Liu-Huan Yi , Shi-Yao Li , Fangfang Du , Liu-Pan Yang , Li-Li Wang . Ultra-highly selective recognition of nucleosides over nucleotides by rational modification of tetralactam macrocycle and its application in enzyme assay. Chinese Chemical Letters, 2024, 35(6): 109154-. doi: 10.1016/j.cclet.2023.109154
3. [3]
  Changhui Yu , Peng Shang , Huihui Hu , Yuening Zhang , Xujin Qin , Linyu Han , Caihe Liu , Xiaohan Liu , Minghua Liu , Yuan Guo , Zhen Zhang . Evolution of template-assisted two-dimensional porphyrin chiral grating structure by directed self-assembly using chiral second harmonic generation microscopy. Chinese Chemical Letters, 2024, 35(10): 109805-. doi: 10.1016/j.cclet.2024.109805
4. [4]
  Shengkai Li , Yuqin Zou , Chen Chen , Shuangyin Wang , Zhao-Qing Liu . Defect engineered electrocatalysts for C–N coupling reactions toward urea synthesis. Chinese Chemical Letters, 2024, 35(8): 109147-. doi: 10.1016/j.cclet.2023.109147
5. [5]
  Kun Tang , Fen Su , Shijie Pan , Fengfei Lu , Zhongfu Luo , Fengrui Che , Xingxing Wu , Yonggui Robin Chi . Enones from aldehydes and alkenes by carbene-catalyzed dehydrogenative couplings. Chinese Chemical Letters, 2024, 35(9): 109495-. doi: 10.1016/j.cclet.2024.109495
6. [6]
  Chaochao Jin , Kai Li , Jiongpei Zhang , Zhihua Wang , Jiajing Tan . N,O-Bidentated difluoroboron complexes based on pyridine-ester enolates: Facile synthesis, post-complexation modification, optical properties, and applications. Chinese Chemical Letters, 2024, 35(9): 109532-. doi: 10.1016/j.cclet.2024.109532
7. [7]
  Yujuan Zhao , Zaiwang Zhao . Monolayer mesoporous nanosheets with surface asymmetry via a dual-emulsion-directed monomicelle assembly. Chinese Journal of Structural Chemistry, 2024, 43(2): 100238-100238. doi: 10.1016/j.cjsc.2024.100238
8. [8]
  Peng Zhou , Ziang Jiang , Yang Li , Peng Xiao , Feixiang Wu . Sulphur-template method for facile manufacturing porous silicon electrodes with enhanced electrochemical performance. Chinese Chemical Letters, 2024, 35(8): 109467-. doi: 10.1016/j.cclet.2023.109467
9. [9]
  Hong-Jin Liao , Zhu Zhuo , Qing Li , Yoshihito Shiota , Jonathan P. Hill , Katsuhiko Ariga , Zi-Xiu Lu , Lu-Yao Liu , Zi-Ang Nan , Wei Wang , You-Gui Huang . A new class of crystalline X-ray induced photochromic materials assembled from anion-directed folding of a flexible cation. Chinese Chemical Letters, 2024, 35(8): 109052-. doi: 10.1016/j.cclet.2023.109052
10. [10]
  Wenling Yuan , Fengli Li , Zhe Chen , Qiaoxin Xu , Zhenhua Guan , Nanyu Yao , Zhengxi Hu , Junjun Liu , Yuan Zhou , Ying Ye , Yonghui Zhang . AbnI: An α-ketoglutarate-dependent dioxygenase involved in brassicicene CH functionalization and ring system rearrangement. Chinese Chemical Letters, 2024, 35(5): 108788-. doi: 10.1016/j.cclet.2023.108788
11. [11]
  Jing-Qi Tao , Shuai Liu , Tian-Yu Zhang , Hong Xin , Xu Yang , Xin-Hua Duan , Li-Na Guo . Photoinduced copper-catalyzed alkoxyl radical-triggered ring-expansion/aminocarbonylation cascade. Chinese Chemical Letters, 2024, 35(6): 109263-. doi: 10.1016/j.cclet.2023.109263
12. [12]
  Yue Sun , Liming Yang , Yaohang Cheng , Guanghui An , Guangming Li . Pd(I)-catalyzed ring-opening arylation of cyclopropyl-α-aminoamides: Access to α-ketoamide peptidomimetics. Chinese Chemical Letters, 2024, 35(6): 109250-. doi: 10.1016/j.cclet.2023.109250
13. [13]
  Qiuyun Li , Yannan Zhu , Yining Wang , Gang Qi , Wen-Juan Hao , Kelu Yan , Bo Jiang . Catalytic CH activation-initiated transdiannulation: An oxygen transfer route to ring-fluorinated tricyclic γ-lactones. Chinese Chemical Letters, 2024, 35(9): 109494-. doi: 10.1016/j.cclet.2024.109494
14. [14]
  Wenyu Gao , Liming Zhang , Chuang Zhao , Lixiang Liu , Xingran Yang , Jinbo Zhao . Controlled semi-Pinacol rearrangement on a strained ring: Efficient access to multi-substituted cyclopropanes by group migration strategy. Chinese Chemical Letters, 2024, 35(9): 109447-. doi: 10.1016/j.cclet.2023.109447
15. [15]
  Pengfei Zhang , Qingxue Ma , Zhiwei Jiang , Xiaohua Xu , Zhong Jin . Transition-metal-catalyzed remote meta-C—H alkylation and alkynylation of aryl sulfonic acids enabled by an indolyl template. Chinese Chemical Letters, 2024, 35(8): 109361-. doi: 10.1016/j.cclet.2023.109361
16. [16]
  Huimin Luan , Qinming Wu , Jianping Wu , Xiangju Meng , Feng-Shou Xiao . Templates for the synthesis of zeolites. Chinese Journal of Structural Chemistry, 2024, 43(4): 100252-100252. doi: 10.1016/j.cjsc.2024.100252
17. [17]
  Fei Yin , Erli Yang , Xue Ge , Qian Sun , Fan Mo , Guoqiu Wu , Yanfei Shen . Coupling WO₃₋_x dots-encapsulated metal-organic frameworks and template-free branched polymerization for dual signal-amplified electrochemiluminescence biosensing. Chinese Chemical Letters, 2024, 35(4): 108753-. doi: 10.1016/j.cclet.2023.108753
18. [18]
  Le Ye , Wei-Xiong Zhang . Structural phase transition in a new organic-inorganic hybrid post-perovskite: (N,N-dimethylpyrrolidinium)[Mn(N(CN)2)3]. Chinese Journal of Structural Chemistry, 2024, 43(6): 100257-100257. doi: 10.1016/j.cjsc.2024.100257
19. [19]
  Xingfen Huang , Jiefeng Zhu , Chuan He . Catalytic enantioselective N-silylation of sulfoximine. Chinese Chemical Letters, 2024, 35(4): 108783-. doi: 10.1016/j.cclet.2023.108783
20. [20]
  Zhaojun Liu , Zerui Mu , Chuanbo Gao . Alloy nanocrystals: Synthesis paradigms and implications. Chinese Journal of Structural Chemistry, 2023, 42(11): 100156-100156. doi: 10.1016/j.cjsc.2023.100156

Get Citation

PDF

XML

Metrics

PDF Downloads(1)
Abstract views(323)
HTML views(40)

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