Heteroditopic hexahomotrioxacalix[3]arene receptors that are capable of binding an anion and a cation simultaneously in a cooperative fashion were synthesized. The structure of one of the triamide derivatives was confirmed by single‐crystal X‐ray diffraction. The binding of alkali metals at the lower rim, and the binding of anions (chloride, bromide) at the upper rim, has been investigated by using 1H NMR titration experiments. Alkali metal binding at the lower rim controls the calix cavity. Li+‐ion binding to the lower rim can improve the binding ability of anions at the upper rim amide moiety by a factor of 15, thus suggesting a strong positive allosteric effect for anion recognition. However, when a Na+ cation is bound to the ionophoric site on the lower rim, the calix cavity is changed from a “flattened cone” to a more‐upright form, which is favored for intramolecular hydrogen bonding between the neighboring NH and C?O groups; this change can block the inclusion of anions onto the amide moiety at the upper rim, which strongly suggests a negative allosteric effect of Na+‐ion binding, which controls the cooperative recognition system. 相似文献
Calixarenes bearing optically pure alpha,beta-amino alcohol groups at their lower rim exhibit exceptional and efficient chiral recognition ability in discrimination of racemic mandelic acid, 2,3-dibenzoyltartaric acid and 2-hydroxy-3-methylbutyric acid. [structure: see text] 相似文献
A calix[6]arene has been selectively functionalized by three different groups at the large rim. The strategy relies on the hostguest recognition chemistry of a biomimetic metal complex at the small rim (so-called "funnel complex") and the Huisgen cycloaddition. The intramolecular thermal reaction proceeds with a high efficiency, chemio- and regioselectivity, allowing the monofunctionalization of one aromatic unit among three. Thanks to the high yield and selectivity of the reaction, it can be applied successively twice on the same compound, which opens the route for inherently chiral calix[6]arenes. This methodology not only is of wide potential for obtaining and exploiting calix[6]arenes that are dissymmetrized at the large rim, but also stands as an exemplary strategy for the selective appending of a functional group on a host platform. 相似文献
[formula: see text] A synthetic scheme for the selective functionalization of all-cis (rccc) resorcinarene platform at the "lower rim" was developed. Self-folding and self-complementary cavitands were prepared for molecular recognition and self-assembly, bearing functionality at remote sites. These molecules promise applications on solid support and as polymeric capsules. 相似文献
An 2-aminopyridyl-bridged calix[6]arene on the upper rim fixed in cone conformation (3) was successfully synthesized and its highly selective recognition towards fluoride ion was proved by fluorescent and 1H NMR titration experiments. 相似文献
A novel anthraquinonoidal calix[4]arene derivative was designed and synthesized for the preferential recognition of biologically important zinc in preference to prominently similar cadmium ions and other metal ions via quenching of fluorescence intensity. The stoichiometry of host guest complexation has been determined to be 1:1. The fluorescence changes associated with the recognition event may be attributed to the interaction of zinc ions with the nitrogenous functionality attached at the lower rim of calix[4]arene cavity which allows spatial disposition of the anthraquinonoid segments. 相似文献
Abstract A new family of macrocyclic calix[4]arenes (4a–d) potentially capable of chiral recognition were synthesized by incorporating the chirality inducing moieties, bis α‐amino acylated polyethylene glycols, or tripeptide bis‐Phe Cystine(OMe)2 to the lower rim. 相似文献
[reaction: see text] p-tert-Butylcalix[5]arenes in a fixed cone conformation, endowed with a urea functionality at the upper rim, behave as remarkably efficient abiotic receptors of omega-amino acids and biogenic amines, which are bound with one end of the chain within the pi-basic cavity (primary recognition site) and the other grasped by the secondary hydrogen bonding donor/acceptor binding site. 相似文献
Supramolecular polymeric assemblies represent an emerging, promising class of molecular assemblies with enormous versatility compared with their covalent polymeric counterparts. Although a large number of host–guest motifs have been produced over the history of supramolecular chemistry, only a limited number of recognition motifs have been utilized as supramolecular connections in polymeric assemblies. This account describes the molecular recognition of host molecules based on calix[5]arene and bisporphyrin that demonstrate unique guest encapsulations; subsequently, these host–guest motifs are applied to the synthesis of supramolecular polymers that display polymer‐like properties in solution and solid states. In addition, new bisresorcinarenes are developed to form supramolecular polymers that are connected via a rim‐to‐rim hydrogen‐bonded dimeric structure, which is composed of two resorcinarene moieties.