The complexation behaviors of anthracenecarboxylic acid and water-soluble cationic pillararenes have been investigated by 1H NMR,UV-vis and ITC methods.The cationic pillar[6]arene was found to stepwise form 1：1 and 1...The complexation behaviors of anthracenecarboxylic acid and water-soluble cationic pillararenes have been investigated by 1H NMR,UV-vis and ITC methods.The cationic pillar[6]arene was found to stepwise form 1：1 and 1：2 complexes,having a large K1 and a relatively small K2 values.Photocyclodimerization of AC within the pillar[6]arene improved the yield of the head-to-head photodimers.Up to 4.97 HH/HT ratio has been reached by optimizing the reaction conditions.展开更多
Photochromic diarylethenes were deemed to be one of the most promising molecular building blocks tot photoresponsive materials. This review gives a brief summary to the recent progress of studies of diarylethenes in s...Photochromic diarylethenes were deemed to be one of the most promising molecular building blocks tot photoresponsive materials. This review gives a brief summary to the recent progress of studies of diarylethenes in supramolecular systems, focusing on their applications in biological systems, photoresponsive mechanical materials and photoresponsive chemosensors. ~ 2015 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.展开更多
Four pillar[5]arene-based bicyclic compounds,so-called molecular universal joint(MUJ),were synthesized by incorporating a bisamide ring containing N,O,or S-heteroatom groups,which served as stimuli-responsive chiropti...Four pillar[5]arene-based bicyclic compounds,so-called molecular universal joint(MUJ),were synthesized by incorporating a bisamide ring containing N,O,or S-heteroatom groups,which served as stimuli-responsive chiroptical molecular devices.The structure of MUJ was confirmed by 1H NMR spectra and single-crystal X-ray diffraction analysis,and their planar-chiral enantiomers were successfully separated.Chiroptical inversion behaviors from in to out configurations triggered by temperature,solvent,and vip complexation were investigated by circular dichroism spectra.Chiroptical inversion could be realized in the presence of adiponitrile in certain solvents due to the solvation effects on the side ring and the threading of the vip into the pillar[5]arene cavity.However,the stronger self-included interactions between the cavity and the inside ring of certain MUJs led to inhibition of the switching.展开更多
Several cyclodextrin-cucurbit[6]uril-cowheeled [4]rotaxanes were synthesized through the cucurbit[6]uril-templated azide-alkyne 1,3-dipolar cycloaddition. The intramolecular interaction between the aromatic axle and t...Several cyclodextrin-cucurbit[6]uril-cowheeled [4]rotaxanes were synthesized through the cucurbit[6]uril-templated azide-alkyne 1,3-dipolar cycloaddition. The intramolecular interaction between the aromatic axle and the capping groups of cyclodextrin moieties was investigated by UV-vis, fluorescence,circular dichroism and NMR spectroscopic studies. The rotational kinetic of the wheel around the axle can be manipulated by adjusting the temperature. The capping group apparently slowed down the rotation of the wheel, playing a role of the brake, and lowering the temperature can stop the rotation of the wheel on the NMR timescale.展开更多
While extensive research has explored manipulating supramolecular chirality through internal and external factors,the specific solvation effect remains uncharted territory.This study synthesized ortho-functionalized p...While extensive research has explored manipulating supramolecular chirality through internal and external factors,the specific solvation effect remains uncharted territory.This study synthesized ortho-functionalized pillar[5]arene(P[5])derivatives Mn and Dn via thiol-Michael addition,characterizing them through spectroscopic and X-ray single-crystal analyses.Mn and Dn interacted with chiral amines,yielding significant circular dichroism(CD)responses.Intriguingly,the chiral induction exhibited pronounced specific solvation effects,where achiral alcohols either enhanced,attenuated,or reversed CD signals.Testing over 40 alcohols revealed correlations between the specific solvation effects and alcohol polarity and acidity.Molecular dynamics simulations unveiled that the alcohol interacted distinctly through hydrogen bonding,with one ion pair bonding up to four alcohol molecules.The Rp-and Sp-preference of the P[5]core could be altered by the number of bonded alcohols.This work uncovers the critical role of alcohol-specific solvation in ion pair-involved chiral assembly,pertinent for asymmetric ion-pairing catalysis and the use of alcohol additives in organic solvents.展开更多
Several novel macrocyclic arenes that are composed of six indole subunits,so-called bisindole[3]arenes(BID[3]s),were conveniently synthesized by the aluminum trichloride-catalyzed one-pot condensation of bisindole der...Several novel macrocyclic arenes that are composed of six indole subunits,so-called bisindole[3]arenes(BID[3]s),were conveniently synthesized by the aluminum trichloride-catalyzed one-pot condensation of bisindole derivatives and paraformaldehyde in dichloromethane at room temperature.Their macrocyclic structures were demonstrated by X-ray single-crystal studies,and the presence of the macrocyclic cavities made it possible to accommodate specific small organic molecules.The BID[3]s have exceptionally high iodine adsorption ability due to the strong and synergic interaction of indole units toward iodine,exhibiting significant morphology changes upon adsorption and desorption of iodine.Iodine uptake capacity of up to 5.12 g·g^(−1) was found with MeBID[3],which is the highest value ever reported for macrocyclic arenes.展开更多
基金supported by the grants from National Natural Science Foundation of China (Nos. 21372165, 21321061 and 21572142 for CY, No. 21402129 for WW)State Key Laboratory of Polymer Materials Engineering (No. sklpme2014-2-06)
文摘The complexation behaviors of anthracenecarboxylic acid and water-soluble cationic pillararenes have been investigated by 1H NMR,UV-vis and ITC methods.The cationic pillar[6]arene was found to stepwise form 1：1 and 1：2 complexes,having a large K1 and a relatively small K2 values.Photocyclodimerization of AC within the pillar[6]arene improved the yield of the head-to-head photodimers.Up to 4.97 HH/HT ratio has been reached by optimizing the reaction conditions.
基金the National Natural Science Foundation of China (Nos. 21372165, 21321061 and 21402129)State Key Laboratory of Polymer Materials Engineering (No. sklpme20142-06)Comprehensive Training Platform of Specialized Laboratory, College of Chemistry, Sichuan University for financial support
文摘Photochromic diarylethenes were deemed to be one of the most promising molecular building blocks tot photoresponsive materials. This review gives a brief summary to the recent progress of studies of diarylethenes in supramolecular systems, focusing on their applications in biological systems, photoresponsive mechanical materials and photoresponsive chemosensors. ~ 2015 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.
基金the National Natural Science Foundation of China(Nos.92056116,21871194,21971169)National Key Research and Development Program of China(No.2017YFA0505903).
文摘Four pillar[5]arene-based bicyclic compounds,so-called molecular universal joint(MUJ),were synthesized by incorporating a bisamide ring containing N,O,or S-heteroatom groups,which served as stimuli-responsive chiroptical molecular devices.The structure of MUJ was confirmed by 1H NMR spectra and single-crystal X-ray diffraction analysis,and their planar-chiral enantiomers were successfully separated.Chiroptical inversion behaviors from in to out configurations triggered by temperature,solvent,and vip complexation were investigated by circular dichroism spectra.Chiroptical inversion could be realized in the presence of adiponitrile in certain solvents due to the solvation effects on the side ring and the threading of the vip into the pillar[5]arene cavity.However,the stronger self-included interactions between the cavity and the inside ring of certain MUJs led to inhibition of the switching.
基金support of this work by the National Natural Science Foundation of China (Nos. 21871194, 21572142, 21372165, 21402129 and 21402110)National Key Research and Development Program of China(No. 2017YFA0505903)+1 种基金Science & Technology Department of Sichuan Province(No. 2017SZ0021)Comprehensive Training Platform of Specialized Laboratory, College of Chemistry, Sichuan university
文摘Several cyclodextrin-cucurbit[6]uril-cowheeled [4]rotaxanes were synthesized through the cucurbit[6]uril-templated azide-alkyne 1,3-dipolar cycloaddition. The intramolecular interaction between the aromatic axle and the capping groups of cyclodextrin moieties was investigated by UV-vis, fluorescence,circular dichroism and NMR spectroscopic studies. The rotational kinetic of the wheel around the axle can be manipulated by adjusting the temperature. The capping group apparently slowed down the rotation of the wheel, playing a role of the brake, and lowering the temperature can stop the rotation of the wheel on the NMR timescale.
基金supported by the National Natural Science Foundation of China(22471182,22271201,92056116,22422108,22171194,22201194)the Fundamental Research Funds for the Central Universities(20826041D4117).
文摘While extensive research has explored manipulating supramolecular chirality through internal and external factors,the specific solvation effect remains uncharted territory.This study synthesized ortho-functionalized pillar[5]arene(P[5])derivatives Mn and Dn via thiol-Michael addition,characterizing them through spectroscopic and X-ray single-crystal analyses.Mn and Dn interacted with chiral amines,yielding significant circular dichroism(CD)responses.Intriguingly,the chiral induction exhibited pronounced specific solvation effects,where achiral alcohols either enhanced,attenuated,or reversed CD signals.Testing over 40 alcohols revealed correlations between the specific solvation effects and alcohol polarity and acidity.Molecular dynamics simulations unveiled that the alcohol interacted distinctly through hydrogen bonding,with one ion pair bonding up to four alcohol molecules.The Rp-and Sp-preference of the P[5]core could be altered by the number of bonded alcohols.This work uncovers the critical role of alcohol-specific solvation in ion pair-involved chiral assembly,pertinent for asymmetric ion-pairing catalysis and the use of alcohol additives in organic solvents.
基金supported by the National Natural Science Foundation of China(nos.21871194,21971169,and 21572142)National Key Research and Development Program of China(no.2017YFA0505903).
文摘Several novel macrocyclic arenes that are composed of six indole subunits,so-called bisindole[3]arenes(BID[3]s),were conveniently synthesized by the aluminum trichloride-catalyzed one-pot condensation of bisindole derivatives and paraformaldehyde in dichloromethane at room temperature.Their macrocyclic structures were demonstrated by X-ray single-crystal studies,and the presence of the macrocyclic cavities made it possible to accommodate specific small organic molecules.The BID[3]s have exceptionally high iodine adsorption ability due to the strong and synergic interaction of indole units toward iodine,exhibiting significant morphology changes upon adsorption and desorption of iodine.Iodine uptake capacity of up to 5.12 g·g^(−1) was found with MeBID[3],which is the highest value ever reported for macrocyclic arenes.
