0000000000202525

AUTHOR

Luzhi Liu

Efficient synthesis of copillar[5]arenes and their host–guest properties with dibromoalkanes

An efficient method for the synthesis of copillar[5]arenes was developed with FeCl(3) as catalyst and different 1,4-dialkoxybenzenes and paraformaldehyde as reactants (yields: 50-85%). The host-guest property of (co)pillar[5]arenes and terminal dibromoalkanes was investigated by (1)H NMR measurements and an X-ray study. The complexation behavior of the copillar[5]arenes can be tuned by changing the substituents on the host. A complete complexation selectivity was found between pillar[5]- and pillar[6]arenes, which is an interesting aspect for sensor techniques.

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Complexation Selectivities of Pillar[5]arenes with Primary Ammonium Salts

The complexation of alkyl-substituted pillar[5]arenes with primary ammonium salts is investigated. 1,4-Bis(methoxy)pillar[5]arene (MeP5) can form strong complexes with the primary ammonium salts in CDCl3. However, 1,4-bis(ethoxy)pillar[5]arene (EtP5) shows weak interaction with these guests, and 1,4-bis(butoxy)pillar[5]arene (BuP5) can not form such a complex at all. These results indicate that the modified alkyl chains of pillar[5]arene play an important role in the complexation selectivity.

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Dimerization control in the self-assembly behavior of copillar[5]arenes bearing ω-hydroxyalkoxy groups.

Two novel copillar[5]arenes bearing ω-hydroxyalkoxy groups are synthesized and their self-assembly properties are studied by (1)H NMR spectroscopy, specific viscosity, and X-ray measurements. The copillar[5]arene 2b bearing a 6-hydroxyhexyloxy group exhibits a reversible self-assembly behavior, leading to the formation of the self-inclusion monomer and hugging dimers. The reversible self-assembly behavior can be controlled by tuning solvent, temperature, guest, and H-bond interaction. However, the copillar[5]arene 2a bearing a short 4-hydroxybutyloxy group does not show such a self-assembly behavior to the formation of the self-inclusion monomer and hugging dimers.

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Crystal Structure and Host-Guest Binding Ability of Three Types of Pillar[5]arenes

A systematic research of the structural characterization and the host-guest binding abilities between three types of pillar[5]arenes 3–5 (3 for Structure Type I, 4 for Structure Type II and 5 for Structure Type III) is carried out by 1H NMR measurements and X-ray study. The results show that the configurations or symmetry of their cavities not only have large difference in these three types of pillar[5]arenes, but also have more or less variations even in the same structure type or the same host locked different guests such as crystals of 3a–3b, 4a–4d. On the other hand, the complexation behavior of pillar[5]arenes with 1,4-dibromobutane (DBB) is affected by the different symmetrical struct…

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CCDC 821446: Experimental Crystal Structure Determination

Related Article: Luzhi Liu, Derong Cao, Yi Jin, Hongqi Tao, Yuhui Kou, H.Meier|2011|Org.Biomol.Chem.|9|7007|doi:10.1039/c1ob05871a

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CCDC 882877: Experimental Crystal Structure Determination

Related Article: Luzhi Liu, Lingyun Wang, Changchun Liu, Zhiyong Fu, Herbert Meier, and Derong Cao|2012|J.Org.Chem.|77|9413|doi:10.1021/jo301779y

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