Design, synthesis and applications of responsive macrocycles

Yu, Jen‐te; Qi, Dawei; Li, Jianwei

doi:10.1038/s42004-020-00438-2

Cited by 66 publications

(58 citation statements)

References 79 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Such macrocycles bear additional functionalities to make them sensitive to external stimuli, e.g., pH, potential, light, etc. Often, a azobenzene moiety is attached as a peripheral or inherent part due to its photo or redox activity [ 8 , 9 , 10 , 11 , 12 ].…”

Section: Introductionmentioning

confidence: 99%

Products of Photo- and Thermochemical Rearrangement of 19-Membered di-tert-Butyl-Azoxybenzocrown

et al. 2022

View full text Add to dashboard Cite

The preparation and characterization of products of the photochemical and thermochemical rearrangements of 19-membered azoxybenzocrowns with two, bulky, tert-butyl substituents in benzene rings in the para positions to oligooxyethylene fragments (meta positions to azoxy group, i.e., t-Bu-19-Azo-O have been presented. In photochemical rearrangement, two colored typical products were expected, i.e., 19-membered o-hydroxy-m,m′-di-tert-butyl-azobenzocrown (t-Bu-19-o-OH) and 19-membered p-hydroxy-m,m′-di-tert-butyl-azobenzocrown (t-Bu-19-p-OH). In experiments, two colored atypical macrocyclic derivatives, one 6-membered and one 5-membered ring, bearing an aldehyde group (t-Bu-19-al) or intramolecular ester group (t-Bu-20-ester), were obtained. Photochemical rearrangement led to one more macrocyclic product being isolated and identified: a 17-membered colorless compound, without an azo moiety, t-Bu-17-p-OH. The yield of the individual compounds was significantly influenced by the reaction conditions. Thermochemical rearrangement led to t-Bu-20-ester as the main product. The structures of the four crystalline products of the rearrangement—t-Bu-19-o-OH, t-Bu-19-p-OH, t-Bu-20-ester and t-Bu-17-p-OH—were determined by the X-ray method. Structures in solution of atypical derivatives (t-Bu-19-al and t-Bu-20-ester) and t-Bu-19-p-OH were defined using NMR spectroscopy. For the newly obtained hydroxyazobenzocrowns, the azo–phenol⇄quinone–hydrazone tautomeric equilibrium was investigated using spectroscopic methods. Complexation studies of alkali and alkaline earth metal cations were studied using UV-Vis absorption spectroscopy. 1H NMR spectroscopy was additionally used to study the cation recognition of metal cations. Cation binding studies in acetonitrile have shown high selectivity towards calcium over magnesium for t-Bu-19-o-OH.

show abstract

Section: Introductionmentioning

confidence: 99%

Products of Photo- and Thermochemical Rearrangement of 19-Membered di-tert-Butyl-Azoxybenzocrown

et al. 2022

View full text Add to dashboard Cite

show abstract

“…The synthesis of azo-calix [4]arene derivatives bearing azobenzoic acid or azobenzenesulfonic acid fragments (compounds 1 and 2, Scheme 2) was carried out using methods from the literature [17,18]. Since the "covalent" method suffers from a complicated molecular design and timeconsuming synthesis of the corresponding fluorescent probes, the "non-covalent" approach using host-guest chemistry is much easier (Scheme 1) [13,14]. In the past two years, the "noncovalent" approach using the host-guest complex of an anionic carboxylate calix [4]arene azo derivative and positively charged dye (rhodamine 123) was successfully used for hypoxia imaging in living cells [15].…”

Section: Resultsmentioning

confidence: 99%

“…Compound 4 was obtained after refluxing the reaction mixture for 18 h with 80% yield. The structure of 4 was well established using 1D NMR 1 H and 13 C spectroscopy, as well as IR spectroscopy and highresolution ESI mass spectrometry (HRESI). NMR signal assignment was performed using 2D NOESY 1 H-1 H spectroscopy.…”

Section: Resultsmentioning

confidence: 99%

Azocalix[4]arene-Rhodamine Supramolecular Hypoxia-Sensitive Systems: A Search for the Best Calixarene Hosts and Rhodamine Guests

et al. 2021

View full text Add to dashboard Cite

A potential hypoxia-sensitive system host-guest complex of three calixarenes (including two with four anionic carboxyl and sulphonate azo fragments on the upper rim and a newly synthesized bis-azo adduct of calixarene in the cone configuration with azo fragments on the lower rim with the most widespread cationic and zwitterionic rhodamine dyes (123, 6G and B)) was studied using UV-VIS spectrometry and fluorescence as well as 1D and 2D NMR techniques. It was found that all three calixarenes form a complex with rhodamine dyes with a 1:1 composition. The association constants of calixarene-dye complexes with sulfonate calixarenes, especially in the case of tetra-anionic calixarene, turned out to be higher compared with carboxyl calixarene due to the more intense electrostatic interactions. For the first time using an HRESI MS technique, it was shown that the treatment of rhodamine 6G and 123 with sodium dithionite (SDT) produces a non-fluorescent leuco form of the dye, and only rhodamine B can be used with SDT without the occurrence of a side reduction. Moreover, it was identified that in addition to the reduction in the azo groups, SDT causes partial cleavage of the aryl ether bonds. The found features of SDT should be taken into account when SDT is used as an azoreductase mimic.

show abstract

“…Lesser developed however, is the incorporation of the 1,1‘‐substituted ferrocene moiety into highly conjugated macrocycles which contain unsaturated linking groups. These molecules exhibit both rigid structures and well‐defined pores, which lend them towards effective application in the areas of sensing and host‐guest chemistry [63–67] . Additionally, the unsaturated nature of the connections within these systems often allows electrons to conjugate their entire length, encouraging studies of global aromaticity and optoelectronic applications [68–72] …”

Section: Introductionmentioning

confidence: 99%

Development and Characterisation of Highly Conjugated Functionalised Ferrocenylene Macrocycles

2022

View full text Add to dashboard Cite

Multiple synthetic pathways were explored for the preparation of ethynylarene-containing ferrocenylene macrocyles. Accordingly, the synthesis of novel bis-and tris-ferrocenylene macrocycles, containing a diethynylpyridine bridging group was achieved, and evidence is also provided for a number of linearanalogues formed as by-products. The electrochemical properties of the macrocycles were examined, and it was shown that the number of observable redox processes does not necessarily correlate with the number of redox active centres. Additionally, examination of the comproportionation constants of the trisferrocenylene macrocycle demonstrated that the monocationic and dicationic species could be assigned to class II and I/II borderline of the Robin-Day classification, respectively. The synthesis of these molecules presents an opportunity towards the development of conjugated ferrocenylene macrocycles for electronic applications.

show abstract

Design, synthesis and applications of responsive macrocycles

Cited by 66 publications

References 79 publications

Products of Photo- and Thermochemical Rearrangement of 19-Membered di-tert-Butyl-Azoxybenzocrown

Products of Photo- and Thermochemical Rearrangement of 19-Membered di-tert-Butyl-Azoxybenzocrown

Azocalix[4]arene-Rhodamine Supramolecular Hypoxia-Sensitive Systems: A Search for the Best Calixarene Hosts and Rhodamine Guests

Development and Characterisation of Highly Conjugated Functionalised Ferrocenylene Macrocycles

Contact Info

Product

Resources

About