7.4
Concluding Remarks
In summary, recent advances in synthetic macrocyclic arenes closely related to
calixarenes and pillarenes have been highlighted in this chapter. These macrocycles
include calix[2]arene[2]triazines, calix[n]imidazoliums, TPE-based oxacalixarenes,
hybrid[n]arenes, calix[3]carbazole, cyclo[4]carbazole, calix[n]triazoles, calix[n]
tetrarenes, coumarin[4]arene, asararenes, biphenarenes, cyanostars, campestarenes,
oxatub[n]arenes, biphenyl-extended pillarenes, pillar[4]pyridinium, and leaning
towerarenes. Although most of the current researches still center on the structural
design and synthetic methodology, the research on their variety of functions is still
yet to be exploited. But, all of them will certainly enrich the toolbox of supramolecular macrocyclic chemistry and indeed unleash new opportunities in future
supramolecular chemistry research. In our lab, we are now in the processes of
functionalizing the extended pillarenes for detection of environmentally harmful
ions and modifying leaning pillar[6]arenes to obtain stimuli-responsive supramolecular polymers and smart hybrid nanomaterials. In any event, for gaining broad
attention by researchers, synthetic macrocycles should at least possess features as
follows: (i) easy accessibility and low price, (ii) unique geometries, (iii) special and
selective binding properties, and (iv) ease of modification. We strongly believe that
all the macrocyclic arenes covered in this chapter possess unlimited potentials and
great possibilities in finding more and more applications.
Acknowledgments We thank the National Natural Science Foundation of China (21871108,
51673084), Jilin Province-University Cooperative Construction Project – Special Funds for New
Materials (SXGJSF2017-3) – Jilin University Talents Cultivation Program, and the JLU Cultivation
Fund for the National Science Fund for Distinguished Young Scholars for financial support.
References
1. Lehn JM (1993) Supramolecular chemistry. Science 260:1762
2. Hargrove AE, Nieto S, Zhang T, Sessler JL, Anslyn EV (2011) Artificial receptors for the
recognition of phosphorylated molecules. Chem Rev 111:6603–6782
3. Yang YW, Sun YL, Song N (2014) Switchable host-guest systems on surfaces. Acc Chem Res
47:1950–1960
4. Jie K, Zhou Y, Yao Y, Huang F (2015) Macrocyclic amphiphiles. Chem Soc Rev 44:3568–3587
5. Liu Z, Nalluri SKM, Stoddart JF (2017) Surveying macrocyclic chemistry: from flexible crown
ethers to rigid cyclophanes. Chem Soc Rev 46:2459–2478
6. Pedersen CJ (1967) Cyclic Polyethers and their complexes with metal salts. J Am Chem Soc
89:2495–2596
7. Pedersen CJ (1967) Cyclic Polyethers and their complexes with metal salts. J Am Chem Soc 89:
7017–7036
8. Bell TW, Firestone A (1986) Torands: rigid toroidal macrocycles. Calcium sequestration by a
member of this new ligand class. J Am Chem Soc 108:8109–8111
9. Ramaiah D, Neelakandan PP, Nair AK, Avirah RR (2010) Functional cyclophanes: promising
hosts for optical biomolecular recognition. Chem Soc Rev 39:4158–4168
10. Barnes JC, Juricek M, Vermeulen NA, Dale EJ, Stoddart JF (2013) Synthesis of Ex(n)Box
cyclophanes. J Org Chem 78:11962–11969
196
D. Dai et al.
Concluding Remarks
In summary, recent advances in synthetic macrocyclic arenes closely related to
calixarenes and pillarenes have been highlighted in this chapter. These macrocycles
include calix[2]arene[2]triazines, calix[n]imidazoliums, TPE-based oxacalixarenes,
hybrid[n]arenes, calix[3]carbazole, cyclo[4]carbazole, calix[n]triazoles, calix[n]
tetrarenes, coumarin[4]arene, asararenes, biphenarenes, cyanostars, campestarenes,
oxatub[n]arenes, biphenyl-extended pillarenes, pillar[4]pyridinium, and leaning
towerarenes. Although most of the current researches still center on the structural
design and synthetic methodology, the research on their variety of functions is still
yet to be exploited. But, all of them will certainly enrich the toolbox of supramolecular macrocyclic chemistry and indeed unleash new opportunities in future
supramolecular chemistry research. In our lab, we are now in the processes of
functionalizing the extended pillarenes for detection of environmentally harmful
ions and modifying leaning pillar[6]arenes to obtain stimuli-responsive supramolecular polymers and smart hybrid nanomaterials. In any event, for gaining broad
attention by researchers, synthetic macrocycles should at least possess features as
follows: (i) easy accessibility and low price, (ii) unique geometries, (iii) special and
selective binding properties, and (iv) ease of modification. We strongly believe that
all the macrocyclic arenes covered in this chapter possess unlimited potentials and
great possibilities in finding more and more applications.
Acknowledgments We thank the National Natural Science Foundation of China (21871108,
51673084), Jilin Province-University Cooperative Construction Project – Special Funds for New
Materials (SXGJSF2017-3) – Jilin University Talents Cultivation Program, and the JLU Cultivation
Fund for the National Science Fund for Distinguished Young Scholars for financial support.
References
1. Lehn JM (1993) Supramolecular chemistry. Science 260:1762
2. Hargrove AE, Nieto S, Zhang T, Sessler JL, Anslyn EV (2011) Artificial receptors for the
recognition of phosphorylated molecules. Chem Rev 111:6603–6782
3. Yang YW, Sun YL, Song N (2014) Switchable host-guest systems on surfaces. Acc Chem Res
47:1950–1960
4. Jie K, Zhou Y, Yao Y, Huang F (2015) Macrocyclic amphiphiles. Chem Soc Rev 44:3568–3587
5. Liu Z, Nalluri SKM, Stoddart JF (2017) Surveying macrocyclic chemistry: from flexible crown
ethers to rigid cyclophanes. Chem Soc Rev 46:2459–2478
6. Pedersen CJ (1967) Cyclic Polyethers and their complexes with metal salts. J Am Chem Soc
89:2495–2596
7. Pedersen CJ (1967) Cyclic Polyethers and their complexes with metal salts. J Am Chem Soc 89:
7017–7036
8. Bell TW, Firestone A (1986) Torands: rigid toroidal macrocycles. Calcium sequestration by a
member of this new ligand class. J Am Chem Soc 108:8109–8111
9. Ramaiah D, Neelakandan PP, Nair AK, Avirah RR (2010) Functional cyclophanes: promising
hosts for optical biomolecular recognition. Chem Soc Rev 39:4158–4168
10. Barnes JC, Juricek M, Vermeulen NA, Dale EJ, Stoddart JF (2013) Synthesis of Ex(n)Box
cyclophanes. J Org Chem 78:11962–11969
196
D. Dai et al.