A series of novel copillar[5]arenes 1a-1f containing different substituents were synthesized.And their com-plexation with two types of guests was investigated.For symmetrical guests,1,4-dibromobutane(DBB)could thread ...A series of novel copillar[5]arenes 1a-1f containing different substituents were synthesized.And their com-plexation with two types of guests was investigated.For symmetrical guests,1,4-dibromobutane(DBB)could thread in the cavity of copillar[5]arenes to form inclusion complexes.But for the unsymmetrical guests,copillar-[5]arene 1f bearing 4-(naphthalen-1-yloxy)butoxy could not complex with sec-butyl iodide(SBI)and sec-butyl bromide(SBB)at all,while 1f showed weak interaction with sec-butylamine•HCl(SBA)outside the cavity.These results indicated that the modified group of copillar[5]arene and the symmetry of guest played an important role in the complexation model and selectivity.展开更多
Pagoda[5]arene(P5),which is composed of five 2,6-dimethoxylanthracene(2,6-DMA)subunits bridged by methylene groups at 1,5 positions,was conveniently synthesized in 43%by trifluoroacetic acid(TFA)-catalyzed one-pot con...Pagoda[5]arene(P5),which is composed of five 2,6-dimethoxylanthracene(2,6-DMA)subunits bridged by methylene groups at 1,5 positions,was conveniently synthesized in 43%by trifluoroacetic acid(TFA)-catalyzed one-pot condensation of commercially available 2,6-DMA and paraformaldehyde in 1,2-dichlorobenzene(o-DCB)at room temperature.P5 showed a highly symmetrical pentagonal structure with a large and deep electron-rich cavity,which made it form stable 1∶2 host–guest complexes with various aryl-pyridinium,bipyridinium,and stilbazolium salts in solution.Interestingly,P5 could complex two or even three guests with its intrinsic cavity and the pseudocavity formed by the adjacent macrocycles in solid states.Moreover,the strong intermolecular charge-transfer(ICT)interactions between P5 and the guests were observed.Especially,the complexes formed by P5 and the protonated pyridinium or bipyridinium salts showed acid/base-responsive color changes in solution and remarkable crystalline vapochromic properties by two kinds of processes:from ICT to no ICT and from ICT to enhanced ICT interaction or vice versa.We believe that the easily available P5 with the specific structure and intriguing 1∶2 host–guest complexation can find wide application in supramolecular assemblies and functional materials.展开更多
The mechanism for the conformational conversion of 1,3-dioxane guest encapsulated inside a capsular host was theoretically investigated using semiempirical PM3 method and DFT methods. The free-state process of the con...The mechanism for the conformational conversion of 1,3-dioxane guest encapsulated inside a capsular host was theoretically investigated using semiempirical PM3 method and DFT methods. The free-state process of the conformational conversion of 1,3-dioxane was also investigated to make a comparison between the two different states using the same theory. The influences of the inner phase of the capsule on the conformational conversion of guest molecule were discussed via analyzing the comparative results. It was found that the capsular host could accommodate 1,3-dioxane within its cavity by the weak attractive interactions between host and guest, and it responds to the conformational conversion of guest by the deformation of hydrogen-bonding seam at the middle of the capsule. When entrapped in the capsule, the guest molecule undergoes the conformational conversion from chair form to twist-boat form slower than that under the free condition. The deformation of the capsule is favorable to maximize the attractive interactions between host and guest.展开更多
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 CDC13. Howeve...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 CDC13. 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.展开更多
The host-guest interactions between cyclopentanocucurbit-[6]uril(CyP_(6)Q[6])as host and six alkyl imidazolium hydrochloride as guests(g1,g2,g3,g4,g5,and g6)have been studied by various techniques,such as^(1)H NMR spe...The host-guest interactions between cyclopentanocucurbit-[6]uril(CyP_(6)Q[6])as host and six alkyl imidazolium hydrochloride as guests(g1,g2,g3,g4,g5,and g6)have been studied by various techniques,such as^(1)H NMR spectroscopy,isothermal titration calorimetry,mass spectrometry,and single-crystal X-ray diffraction analysis.The experimental results showed that CyP6Q[6]formed 1:1 inclusion complexes with each of guests g1-g6.The part of the guest entered the cavity of CyP_(6)Q[6]changes as the alkyl chain increases in length.It can be seen that the length of the alkyl chain plays a key role in determining the mode of host-guest interactions.展开更多
Two functionalized calixarenes in cone conformation L 2-3 have been synthesized and their intramolecular inclusion complexes (1∶1) with organic neutral molecules CH 3CN and CH 3NO 2 have been prepared and c...Two functionalized calixarenes in cone conformation L 2-3 have been synthesized and their intramolecular inclusion complexes (1∶1) with organic neutral molecules CH 3CN and CH 3NO 2 have been prepared and characterized, respectively. The X-ray crystallographic analysis shows that L 2 in L 2·CH 3CN·C 2H 5OH has C 4 symmestry and L 3 in L 3·CH 3NO 2 exhibits C 2 symmestry. The CH-π aromatic interactions between the CH group of the guest and the phenyl rings of the calix backbond have been proved to be able to stabilize the intramolecular inclusion complexes formed. The interaction is directional, but it is independent of the acidity of the guest. To gain information on CH-π interactions, suitable geometrical parameters have been calculated from the crystal data of intramolecular inclusion complexes. The results show that L 3·CH 3NO 2 with L 3 in C 2 symmestry can also be bound stably in the intramolecular inclusion complex, being consistent with the thermal analysis. The geometrical parameters and the results of the thermal analysis of L 1·CH 3CN and L 1·CH 3NO 2 were also given and discussed.展开更多
4-Nitro-benzendiazonium (4-NBD) was found to form a 1:1 host-guest complex (NBD@CB) with cucurbit[7]uril (CB[7]) in aqueous solution and 4-NBD enters into the cavity of CB[7] with a binding constant of1.28 x 10~5 L/mo...4-Nitro-benzendiazonium (4-NBD) was found to form a 1:1 host-guest complex (NBD@CB) with cucurbit[7]uril (CB[7]) in aqueous solution and 4-NBD enters into the cavity of CB[7] with a binding constant of1.28 x 10~5 L/mol. NBD@CB can be decomposed into a nitrobenzene/4-nitrophenol mixture in a high total yield (61 %+ 33%) in the presence of CuCl, unlike the decomposition of 4-NBD in the presence of either CB[7] or CuCl, or both absence, where would result in significant amounts of unknown byproducts. This work might provide an economic and effective way to obtain arenes or phenols through the substitution of diazonium salts.展开更多
1 Results In this paper we report supramolecular polymeric nano networks formed by the molecular-recognition-directed self-assembly between a calix[5]arene and C60[1]. Covalently-linked double-calix[5]arenes take up C...1 Results In this paper we report supramolecular polymeric nano networks formed by the molecular-recognition-directed self-assembly between a calix[5]arene and C60[1]. Covalently-linked double-calix[5]arenes take up C60 into their cavities[2]. This complementary interaction creates a strong non-covalent bonding; thus,the iterative self-assembly between dumbbell fullerene 1 and ditopic host 2 can produce the supramolecular polymer networks (See Fig.1).展开更多
A metal-organic photoinduced electron transfer(PET) supramolecular nanoarchitecture comprised of Ru(Ⅱ) bis(terpyridine)-modified pillar[5]arene(electron acceptor) and triazole triphenylamine amyl cyanide(electron don...A metal-organic photoinduced electron transfer(PET) supramolecular nanoarchitecture comprised of Ru(Ⅱ) bis(terpyridine)-modified pillar[5]arene(electron acceptor) and triazole triphenylamine amyl cyanide(electron donor) has been designed and constructed.Through the comparison of diverse solvents and acceptors,the two conditions,i.e.,modification of pillar[5]arene to donor and weak polar solvent are benefit for the occurrence of "efficient PET" because of shorter D-A distance in the presence of pillar[5]arene.Crucially,the fluorescence and PET process of the supramolecular assembly could be further modulated by solvent conversion and another competitive guest.The study provides a supramolecular method to design and construct tunable PET systems and PET-based smart materials.展开更多
基金the National Natural Science Foundation of China(No.21402033)the Guangxi Natural Science Foundation of China(No.2013GXNSFBA019033)+1 种基金the Guangxi Experiment Cen-tre of Science and Technology(No.YXKT2014009)the Scientific Research Foundation of Guangxi University(No.XBZ130017).
文摘A series of novel copillar[5]arenes 1a-1f containing different substituents were synthesized.And their com-plexation with two types of guests was investigated.For symmetrical guests,1,4-dibromobutane(DBB)could thread in the cavity of copillar[5]arenes to form inclusion complexes.But for the unsymmetrical guests,copillar-[5]arene 1f bearing 4-(naphthalen-1-yloxy)butoxy could not complex with sec-butyl iodide(SBI)and sec-butyl bromide(SBB)at all,while 1f showed weak interaction with sec-butylamine•HCl(SBA)outside the cavity.These results indicated that the modified group of copillar[5]arene and the symmetry of guest played an important role in the complexation model and selectivity.
基金The authors thank the National Natural Science Foundation of China(nos.22031010,21772205,21521002,and 91856117)for financial support.
文摘Pagoda[5]arene(P5),which is composed of five 2,6-dimethoxylanthracene(2,6-DMA)subunits bridged by methylene groups at 1,5 positions,was conveniently synthesized in 43%by trifluoroacetic acid(TFA)-catalyzed one-pot condensation of commercially available 2,6-DMA and paraformaldehyde in 1,2-dichlorobenzene(o-DCB)at room temperature.P5 showed a highly symmetrical pentagonal structure with a large and deep electron-rich cavity,which made it form stable 1∶2 host–guest complexes with various aryl-pyridinium,bipyridinium,and stilbazolium salts in solution.Interestingly,P5 could complex two or even three guests with its intrinsic cavity and the pseudocavity formed by the adjacent macrocycles in solid states.Moreover,the strong intermolecular charge-transfer(ICT)interactions between P5 and the guests were observed.Especially,the complexes formed by P5 and the protonated pyridinium or bipyridinium salts showed acid/base-responsive color changes in solution and remarkable crystalline vapochromic properties by two kinds of processes:from ICT to no ICT and from ICT to enhanced ICT interaction or vice versa.We believe that the easily available P5 with the specific structure and intriguing 1∶2 host–guest complexation can find wide application in supramolecular assemblies and functional materials.
基金Supported by the Special Research Fund for the Doctoral Program of Higher Education(No20040010008)the Scientific Research Fund of Beijing University of Chemical Technology(NoQN0411)
文摘The mechanism for the conformational conversion of 1,3-dioxane guest encapsulated inside a capsular host was theoretically investigated using semiempirical PM3 method and DFT methods. The free-state process of the conformational conversion of 1,3-dioxane was also investigated to make a comparison between the two different states using the same theory. The influences of the inner phase of the capsule on the conformational conversion of guest molecule were discussed via analyzing the comparative results. It was found that the capsular host could accommodate 1,3-dioxane within its cavity by the weak attractive interactions between host and guest, and it responds to the conformational conversion of guest by the deformation of hydrogen-bonding seam at the middle of the capsule. When entrapped in the capsule, the guest molecule undergoes the conformational conversion from chair form to twist-boat form slower than that under the free condition. The deformation of the capsule is favorable to maximize the attractive interactions between host and guest.
基金We are grateful to the National Natural Science Foundation of China,the Natural Science Foundation of Guangxi Province
文摘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 CDC13. 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.
基金This work was supported by the National Natural Science Foundation of China(No.21762011)the Guizhou Science and Technology Planning Project,China(Guizhou Science and Technology Cooperation Platform Talent)(No.20175788)the Guizhou Province Graduate Education Innovation Project,China[No.YJSCXJH(2020)188].
文摘The host-guest interactions between cyclopentanocucurbit-[6]uril(CyP_(6)Q[6])as host and six alkyl imidazolium hydrochloride as guests(g1,g2,g3,g4,g5,and g6)have been studied by various techniques,such as^(1)H NMR spectroscopy,isothermal titration calorimetry,mass spectrometry,and single-crystal X-ray diffraction analysis.The experimental results showed that CyP6Q[6]formed 1:1 inclusion complexes with each of guests g1-g6.The part of the guest entered the cavity of CyP_(6)Q[6]changes as the alkyl chain increases in length.It can be seen that the length of the alkyl chain plays a key role in determining the mode of host-guest interactions.
基金theNationalNaturalScienceFoundationofChina (No .2 9872 0 34 )andtheNaturalScienceFoundationofHenan ,China
文摘Two functionalized calixarenes in cone conformation L 2-3 have been synthesized and their intramolecular inclusion complexes (1∶1) with organic neutral molecules CH 3CN and CH 3NO 2 have been prepared and characterized, respectively. The X-ray crystallographic analysis shows that L 2 in L 2·CH 3CN·C 2H 5OH has C 4 symmestry and L 3 in L 3·CH 3NO 2 exhibits C 2 symmestry. The CH-π aromatic interactions between the CH group of the guest and the phenyl rings of the calix backbond have been proved to be able to stabilize the intramolecular inclusion complexes formed. The interaction is directional, but it is independent of the acidity of the guest. To gain information on CH-π interactions, suitable geometrical parameters have been calculated from the crystal data of intramolecular inclusion complexes. The results show that L 3·CH 3NO 2 with L 3 in C 2 symmestry can also be bound stably in the intramolecular inclusion complex, being consistent with the thermal analysis. The geometrical parameters and the results of the thermal analysis of L 1·CH 3CN and L 1·CH 3NO 2 were also given and discussed.
基金financially supported by the National Natural Science Foundation of China (Nos. 21572063 and 21372076)the Science Fund for Creative Research Groups (No. 21421004)+1 种基金the Program of Introducing Talents of Discipline to Universities (No. B16017)the Fundamental Research Funds for the Central Universities (No. 222201717003)
文摘4-Nitro-benzendiazonium (4-NBD) was found to form a 1:1 host-guest complex (NBD@CB) with cucurbit[7]uril (CB[7]) in aqueous solution and 4-NBD enters into the cavity of CB[7] with a binding constant of1.28 x 10~5 L/mol. NBD@CB can be decomposed into a nitrobenzene/4-nitrophenol mixture in a high total yield (61 %+ 33%) in the presence of CuCl, unlike the decomposition of 4-NBD in the presence of either CB[7] or CuCl, or both absence, where would result in significant amounts of unknown byproducts. This work might provide an economic and effective way to obtain arenes or phenols through the substitution of diazonium salts.
文摘1 Results In this paper we report supramolecular polymeric nano networks formed by the molecular-recognition-directed self-assembly between a calix[5]arene and C60[1]. Covalently-linked double-calix[5]arenes take up C60 into their cavities[2]. This complementary interaction creates a strong non-covalent bonding; thus,the iterative self-assembly between dumbbell fullerene 1 and ditopic host 2 can produce the supramolecular polymer networks (See Fig.1).
基金the National Natural Science Foundation of China(Nos.21801063,21672192,21803059 and 21929101)China Postdoctoral Science Foundation(No.2018M642767)+4 种基金Ph.D.Foundation of Henan University of Technology,China(No.2017BS020)the Science and Technology Foundation of Henan Province(No.192102210039)the Colleges and Universities Key Research Program Foundation of Henan Province(No.19A150022)Fundation of Henan University of Technology(No.2018QNJH14)the Natural Science Foundation of Henan Province(No.182300410255)for financial support。
文摘A metal-organic photoinduced electron transfer(PET) supramolecular nanoarchitecture comprised of Ru(Ⅱ) bis(terpyridine)-modified pillar[5]arene(electron acceptor) and triazole triphenylamine amyl cyanide(electron donor) has been designed and constructed.Through the comparison of diverse solvents and acceptors,the two conditions,i.e.,modification of pillar[5]arene to donor and weak polar solvent are benefit for the occurrence of "efficient PET" because of shorter D-A distance in the presence of pillar[5]arene.Crucially,the fluorescence and PET process of the supramolecular assembly could be further modulated by solvent conversion and another competitive guest.The study provides a supramolecular method to design and construct tunable PET systems and PET-based smart materials.