Synthetic macrocyclic host molecules always play an essential role in the establishment and development of supramolecular chemistry. Along with the continuous interests in the study of classical macrocycles, recent de...Synthetic macrocyclic host molecules always play an essential role in the establishment and development of supramolecular chemistry. Along with the continuous interests in the study of classical macrocycles, recent decades have witnessed the emergence and rapid development of the chemistry and supramolecular chemistry of novel and functional macrocycles. Owing to their easy availability, a self-tunable V-shaped cavity resulted from 1,3-alternate conformation, and diversified electronic features steered by the interplay between heteroatom linkages and aromatic rings, heteracalixaromatics act as a type of versatile and powerful macrocyclic hosts in molecular recognition and fabrication of supramolecular systems. Very recently, by means of engineering the bond connectivity or the recombination of chemical bonds within heteracalixaromatics, we have devised coronarenes, a new generation of macrocycles. In this concise review, macrocyclic and supramolecular chemistry of coronarenes are summarized in the order of their syntheses, structural features, molecular recognition and self-assembly properties. In the last part of this article, personal perspectives on the study of macrocyclic and supramolecular chemistry will also be discussed.展开更多
O6-Corona[3]arene[3]pyridazines were synthesized from the one-pot macrocyclic condensation reaction of 3,6-dichlorotetrazine with 1,4-dihydroquinone derivatives followed by the inverse electron demand Diels-Alder reac...O6-Corona[3]arene[3]pyridazines were synthesized from the one-pot macrocyclic condensation reaction of 3,6-dichlorotetrazine with 1,4-dihydroquinone derivatives followed by the inverse electron demand Diels-Alder reaction of the tetrazine rings with a cyclopentanone-derived enamine. Conversion of six ester groups within macrocycle into all sodium acetate moieties afforded a water soluble O6-corona[3]arene[3]pyridazine. The coronary macrocycle host formed complexes selectively with organic ammoniums and dinitrile guests in a 1 ： 1 stoichiometric ratio in organic solvents with association constants ranging from （2.96± 0.10）× 10^1 to （2.53±0.33）× 10^5 L·mol^-1. Water soluble O6-corona[3]arene[3]pyridazine was also able to complex strongly with organic ammoniums in water to give an association constant up to （2.67 ± 0.21） × 10^4 L·mol^-1. The pseudo-rotaxane and inclusion structures of the host-guest complexes were revealed by the X-ray crystallography.展开更多
基金supported by the National Natural Science Foundation of China (21732004, 21421064, 91427301, 21132005)Tsinghua University
文摘Synthetic macrocyclic host molecules always play an essential role in the establishment and development of supramolecular chemistry. Along with the continuous interests in the study of classical macrocycles, recent decades have witnessed the emergence and rapid development of the chemistry and supramolecular chemistry of novel and functional macrocycles. Owing to their easy availability, a self-tunable V-shaped cavity resulted from 1,3-alternate conformation, and diversified electronic features steered by the interplay between heteroatom linkages and aromatic rings, heteracalixaromatics act as a type of versatile and powerful macrocyclic hosts in molecular recognition and fabrication of supramolecular systems. Very recently, by means of engineering the bond connectivity or the recombination of chemical bonds within heteracalixaromatics, we have devised coronarenes, a new generation of macrocycles. In this concise review, macrocyclic and supramolecular chemistry of coronarenes are summarized in the order of their syntheses, structural features, molecular recognition and self-assembly properties. In the last part of this article, personal perspectives on the study of macrocyclic and supramolecular chemistry will also be discussed.
基金We also thank the National Natural Science Foundation of China （Nos. 21732004, 91427301, 21421064） and Tsinghua University for financial Support.
文摘O6-Corona[3]arene[3]pyridazines were synthesized from the one-pot macrocyclic condensation reaction of 3,6-dichlorotetrazine with 1,4-dihydroquinone derivatives followed by the inverse electron demand Diels-Alder reaction of the tetrazine rings with a cyclopentanone-derived enamine. Conversion of six ester groups within macrocycle into all sodium acetate moieties afforded a water soluble O6-corona[3]arene[3]pyridazine. The coronary macrocycle host formed complexes selectively with organic ammoniums and dinitrile guests in a 1 ： 1 stoichiometric ratio in organic solvents with association constants ranging from （2.96± 0.10）× 10^1 to （2.53±0.33）× 10^5 L·mol^-1. Water soluble O6-corona[3]arene[3]pyridazine was also able to complex strongly with organic ammoniums in water to give an association constant up to （2.67 ± 0.21） × 10^4 L·mol^-1. The pseudo-rotaxane and inclusion structures of the host-guest complexes were revealed by the X-ray crystallography.
