12.11 Conclusion
In summary, as new classes of macrocyclic arenes in supramolecular chemistry,
biphen[n]arenes, terphen[n]arenes, and quaterphen[n]arenes have been successfully
designed and constructed. Due to their easy accessibility (one-step synthesis),
π-electron rich cavities, and unique conformation, studies on their functionalization,
molecular recognition, and self-assembly have been explored. For example,
the macrocycles of biphen[n]arenes and their derivatives show good host–guest
complexation abilities toward organic cationic guests and electron-deficient
neutral molecules. The excellent self-assembly properties of long and rigid oligo
(para-phenylenes) monomers of terphen[n]arenes and quaterphen[n]arenes render
them amenable to gelation by self-assembly in organic solvent through
intermolecular πÁÁÁπ interactions.
The investigations of biphen[n]arene, terphen[n]arene, and quaterphen[n]arene
chemistry are just in their infancy. Further studies of these macrocycles are urgently
needed, including various functionalizations of biphen[n]arenes, the molecular recognition between biomacromolecules (i.e., peptides or proteins) and larger cavities
of terphen[n]arenes and quaterphen[n]arenes, and the further derivatization of
terphen[n]arenes and quaterphen[n]arenes. On the other hand, exploration of new
members of extended biphen[n]arene families such as quinquephen[n]arenes and
sexiphen[n]arenes can also be anticipated in the future. Last but not least, we believe
that these macrocyclic arenes will receive increasing attention and that further
research will be performed in the future.
Acknowledgments We thank the National Natural Science Foundation of China (21772118 and
21472121), the Shanghai “Pujiang Program” (16PJD024), and the “Shuguang Program” for the
financial support.
References
1. Barrow SJ, Kasera S, Rowland MJ, del Barrio J, Scherman OA (2015) Cucurbituril based
molecular recognition. Chem Rev 115:12320–12406
2. Jie K, Zhou Y, Yao Y, Huang F (2015) Macrocyclic amphiphiles. Chem Soc Rev 44:3568–3587
3. Alsbaiee A, Smith BJ, Xiao L, Ling Y, Helbling DE, Dichtel WR (2016) Rapid removal of
organic micropollutants from water by a porous β-cyclodextrin polymer. Nature 529:190–194
4. Harada A, Takashima Y, Nakahata M (2014) Supramolecular polymeric materials via
cyclodextrin-guest interactions. Acc Chem Res 47:2128–2140
5. Guo D-S, Liu Y (2012) Calixarene-based supramolecular polymerization in solution. Chem Soc
Rev 41:5907–5921
6. Webber MJ, Appel EA, Meijer EW, Langer R (2015) Supramolecular biomaterials. Nat Mater
15:13–26
7. Li B, Meng Z, Li Q, Huang X, Kang Z, Dong H, Chen J, Sun J, Dong Y, Li J, Jia X, Sessler JL,
Meng Q, Li C (2017) A pH responsive complexation-based drug delivery system for
oxaliplatin. Chem Sci 8:4458–4464
8. Liu Z, Zhang H, Zhao Y (2018) Pillararene-based self-assembled amphiphiles. Chem Soc Rev
47:5491–5528
12 Biphen[n]arenes: Synthesis and Host–Guest Properties
337
In summary, as new classes of macrocyclic arenes in supramolecular chemistry,
biphen[n]arenes, terphen[n]arenes, and quaterphen[n]arenes have been successfully
designed and constructed. Due to their easy accessibility (one-step synthesis),
π-electron rich cavities, and unique conformation, studies on their functionalization,
molecular recognition, and self-assembly have been explored. For example,
the macrocycles of biphen[n]arenes and their derivatives show good host–guest
complexation abilities toward organic cationic guests and electron-deficient
neutral molecules. The excellent self-assembly properties of long and rigid oligo
(para-phenylenes) monomers of terphen[n]arenes and quaterphen[n]arenes render
them amenable to gelation by self-assembly in organic solvent through
intermolecular πÁÁÁπ interactions.
The investigations of biphen[n]arene, terphen[n]arene, and quaterphen[n]arene
chemistry are just in their infancy. Further studies of these macrocycles are urgently
needed, including various functionalizations of biphen[n]arenes, the molecular recognition between biomacromolecules (i.e., peptides or proteins) and larger cavities
of terphen[n]arenes and quaterphen[n]arenes, and the further derivatization of
terphen[n]arenes and quaterphen[n]arenes. On the other hand, exploration of new
members of extended biphen[n]arene families such as quinquephen[n]arenes and
sexiphen[n]arenes can also be anticipated in the future. Last but not least, we believe
that these macrocyclic arenes will receive increasing attention and that further
research will be performed in the future.
Acknowledgments We thank the National Natural Science Foundation of China (21772118 and
21472121), the Shanghai “Pujiang Program” (16PJD024), and the “Shuguang Program” for the
financial support.
References
1. Barrow SJ, Kasera S, Rowland MJ, del Barrio J, Scherman OA (2015) Cucurbituril based
molecular recognition. Chem Rev 115:12320–12406
2. Jie K, Zhou Y, Yao Y, Huang F (2015) Macrocyclic amphiphiles. Chem Soc Rev 44:3568–3587
3. Alsbaiee A, Smith BJ, Xiao L, Ling Y, Helbling DE, Dichtel WR (2016) Rapid removal of
organic micropollutants from water by a porous β-cyclodextrin polymer. Nature 529:190–194
4. Harada A, Takashima Y, Nakahata M (2014) Supramolecular polymeric materials via
cyclodextrin-guest interactions. Acc Chem Res 47:2128–2140
5. Guo D-S, Liu Y (2012) Calixarene-based supramolecular polymerization in solution. Chem Soc
Rev 41:5907–5921
6. Webber MJ, Appel EA, Meijer EW, Langer R (2015) Supramolecular biomaterials. Nat Mater
15:13–26
7. Li B, Meng Z, Li Q, Huang X, Kang Z, Dong H, Chen J, Sun J, Dong Y, Li J, Jia X, Sessler JL,
Meng Q, Li C (2017) A pH responsive complexation-based drug delivery system for
oxaliplatin. Chem Sci 8:4458–4464
8. Liu Z, Zhang H, Zhao Y (2018) Pillararene-based self-assembled amphiphiles. Chem Soc Rev
47:5491–5528
12 Biphen[n]arenes: Synthesis and Host–Guest Properties
337