Co-reporter:Qianfu Luo, Fei Cao, Chaochao Xiong, Qingyu Dou, and Da-Hui Qu
The Journal of Organic Chemistry October 20, 2017 Volume 82(Issue 20) pp:10960-10960
Publication Date(Web):September 22, 2017
DOI:10.1021/acs.joc.7b01877
How to efficiently design and synthesize multifunctional molecules is particularly challenging. In this presentation, we devote to constructing a kind of simple structures with composite functionalities through straightforward preparation. Starting from common commercially available materials, the titled cis/trans-tetraarylethenes can be conveniently obtained by a one-pot process under mild conditions. The different configurations were confirmed by 1H NMR and single crystal data analysis. The trans-tetraarylethenes could be converted into cis-forms not only by photoirradiation but also by microwave irradiation, which provided us a new choice for isomeric conversion, especially in relation to light sensitivity. Results show that all the hybrid cis/trans-isomers performed switchable fluorescence and reversible photochromism in solution, PMMA film, solid powder, and single crystal. Moreover, these hybrid tetraarylethenes could be utilized as photoswitchable media to tune the behavior of aggregation-induced emission (AIE) and aggregation-caused quenching (ACQ). These versatile properties are favorable for the potential applications in fluorescent photoswitches, nondestructive readout, and logic gates. We hope that our design strategy could provide a new protocol for constructing a kind of multifunctional molecules based some simple structure and convenient synthetic procedures.
Co-reporter:Chuan Gao, Zhou-Lin Luan, Qi Zhang, Si-Jia Rao, Da-Hui Qu, and He Tian
Organic Letters July 21, 2017 Volume 19(Issue 14) pp:3931-3931
Publication Date(Web):July 11, 2017
DOI:10.1021/acs.orglett.7b01853
A novel braided hetero[2](3)rotaxane is demonstrated by integrating the braided structure and mechanically interlocked rotaxane, in which a heterotritopic linear tris(dialkylammonium) guest penetrates a heterotritopic tris(crown ether) host, resulting in the formation of braided pseudohetero[2](3)rotaxane with different crossing and threading points. Then a braided hetero[2](3)rotaxane is constructed through the “CuAAC” click reaction.
Co-reporter:Si-Jia Rao;Qi Zhang;Ju Mei;Xu-Hao Ye;Chuan Gao;Qiao-Chun Wang;He Tian
Chemical Science (2010-Present) 2017 vol. 8(Issue 10) pp:6777-6783
Publication Date(Web):2017/09/25
DOI:10.1039/C7SC03232C
In this article, a six-component self-sorting process that involves three types of crown ether macrocycle and three types of cation guest molecule was carefully and thoroughly investigated. The six components include three kinds of crown ether, namely bis(p-phenylene-34-crown-10) (BPP34C10), dibenzo-24-crown-8 (DB24C8) and benzo-21-crown-7 (B21C7), and their corresponding cation guest molecules, namely a 4,4′-bipyridine dication (BPY2+) and dibenzylammonium (DBA) and benzylalkylammonium (BAA) ions, respectively. Based on this well-established highly selective six-component self-sorting process, a hetero[6]rotaxane bearing three different kinds of crown ether macrocycle was designed and successfully synthesized through a facile and efficient one-pot “click” stoppering strategy. Such work is proposed to be a significant advance in the construction of mechanically interlocked molecules with high structural complexity, as well as a good supplement in the areas of multi-component self-sorting and noncovalent self-assembly.
Co-reporter:Zhan-Qi Cao;Yi-Chuan Wang;Ai-Hua Zou;Gábor London;Qi Zhang;Chuan Gao
Chemical Communications 2017 vol. 53(Issue 62) pp:8683-8686
Publication Date(Web):2017/08/01
DOI:10.1039/C7CC05008A
An acid/base responsive amphiphilic [2]rotaxane switch containing a hydrophilic macrocycle component and a hydrophobic terminal bulky group was prepared and characterized. The morphology of the supramolecular assemblies formed by the rotaxanes could be switched between spherical vesicles and worm-like micelles using acid/base stimuli, as confirmed by transmission electron microscopy (TEM).
Co-reporter:Xin Fu, Qi Zhang, Si-Jia Rao, Da-Hui Qu and He Tian
Chemical Science 2016 vol. 7(Issue 3) pp:1696-1701
Publication Date(Web):12 Jan 2016
DOI:10.1039/C5SC04844C
The construction and efficient synthesis of hetero[n]rotaxanes with high structural complexity are always attractive challenges. Herein, we demonstrate a facile one-pot preparation of a hetero[4]rotaxane, by employing a self-sorting strategy, which contains an interpenetrated dibenzo-24-crown-8 (DB24C8) based [c2]daisy chain structure and is ended with a benzo-21-crown-7 (B21C7) based rotaxane at each side. The key to the design involved encoding the selective threading using a steric hindrance-related “language”, where highly selective self-assemblies occurred in a three-component self-sorting process, which included the threading of a benzylalkylammonium into a B21C7 and interpenetrated dimerized formation of a DB24C8 based [c2]daisy chain simultaneously; the precise pre-assembled system resulted in the efficient synthesis of hetero[4]rotaxane with a high-level of structural complexity under the “CuAAC” reaction.
Co-reporter:Zhan-Qi Cao, Zhou-Lin Luan, Qi Zhang, Rui-Rui Gu, Jun Ren and Da-Hui Qu
Polymer Chemistry 2016 vol. 7(Issue 10) pp:1866-1870
Publication Date(Web):04 Feb 2016
DOI:10.1039/C5PY01944C
An acid/base-responsive polyrotaxane system was constructed, in which the side chain was modified with a diferrocene-functionalized bistable rotaxane molecular switch via the “CuAAC” click reaction. The reversible subunit shuttling movement of the rotaxane unit in the polymer system in response to external acid/base stimuli was accompanied by visual fluorescence changes.
Co-reporter:Xin Fu, Rui-Rui Gu, Qi Zhang, Si-Jia Rao, Xiu-Li Zheng, Da-Hui Qu and He Tian
Polymer Chemistry 2016 vol. 7(Issue 12) pp:2166-2170
Publication Date(Web):25 Feb 2016
DOI:10.1039/C6PY00309E
A new strategy for phototriggered supramolecular polymerization of the [c2]daisy chain is demonstrated. A daisy chain rotaxane containing two coumarin protected 2-ureido-4-pyrimidinone (Upy) terminals at two ends was designed, whose supramolecular polymerization can be initiated by light irradiation that can remove the photocleavable protecting coumarin groups and uncage the two terminal Upy functional units.
Co-reporter:Qi Zhang ; Da-Hui Qu
ChemPhysChem 2016 Volume 17( Issue 12) pp:1759-1768
Publication Date(Web):
DOI:10.1002/cphc.201501048
Abstract
Artificial molecular machines have received significant attention from chemists because of their unique ability to mimic the behaviors of biological systems. Artificial molecular machines can be easily modified with functional groups to construct new types of functional molecular switches. However, practical applications of artificial molecular machines are still challenging, because the working platform of artificial molecular machines is mostly in solution. Artificial molecular machine immobilized surfaces (AMMISs) are considered a promising platform to construct functional materials. Herein, we provide a minireview of some recent advances of functional AMMISs. The functions of AMMISs are highlighted and strategies for their construction are also discussed. Furthermore, a brief perspective of the development of artificial molecular machines towards functional materials is given.
Co-reporter:Zhan-Qi Cao, Qi Miao, Qi Zhang, Hong Li, Da-Hui Qu and He Tian
Chemical Communications 2015 vol. 51(Issue 24) pp:4973-4976
Publication Date(Web):12 Jan 2015
DOI:10.1039/C4CC09976A
A fluorescent bistable [2]rotaxane terminated with an alkyne functional group was constructed and immobilized onto the surface of SiO2 nanoparticles through click reaction. The shuttling motion of the macrocycle component between two different stations was driven by external acid–base stimuli both in solution and on SiO2 nanoparticles, accompanied by visual fluorescence changes.
Co-reporter:Ruirui Gu, Jian Yao, Xin Fu, Wei Zhou and Da-Hui Qu
Chemical Communications 2015 vol. 51(Issue 25) pp:5429-5431
Publication Date(Web):18 Nov 2014
DOI:10.1039/C4CC08533G
A hyperbranched supramolecular polymer has been constructed through orthogonal self-crosslinking by two classical binding interactions: triple hydrogen bonding interaction between a three-arm melamine derivative and DB24C8-containing bisimide and host–guest interaction between DB24C8 crown ether and ditopic dibenzyl ammonium moieties.
Co-reporter:Zhan-Qi Cao;Dr. Hong Li;Jian Yao;Dr. Lei Zou;Dr. Da-Hui Qu;Dr. He Tian
Asian Journal of Organic Chemistry 2015 Volume 4( Issue 3) pp:212-216
Publication Date(Web):
DOI:10.1002/ajoc.201402201
Abstract
A bistable bis-branched [3]rotaxane with a perylene bisimide (PBI) chromophore that separates two mechanically interlocked [2]rotaxane arms including a diferrocene-functionalized dibenzo-24-crown-8 ring, was designed, prepared, and characterized by 1H NMR and 13C NMR spectroscopy and HR-ESI mass spectrometry. The uniform relative shuttling movement of target [3]rotaxane in response to external acid-base stimuli was confirmed by 1H NMR spectroscopy. Furthermore, the shuttling motion of the macrocycles in the system was accompanied by a remarkably visual fluorescence change due to the distance-dependent photoinduced electron transfer process from the ferrocene units to the PBI fluorophore. This kind of rotaxane has important potential for designing more sophisticated mechanically interlocked molecules with controllable functions.
Co-reporter:Qi Zhang; Da-Hui Qu; Qiao-Chun Wang ; He Tian
Angewandte Chemie International Edition 2015 Volume 54( Issue 52) pp:15789-15793
Publication Date(Web):
DOI:10.1002/anie.201509071
Abstract
The realization of controllable multicomponent self-assembly through reversible supramolecular interactions is a challenging goal, and is an important strategy for the fabrication of switchable nanomaterials. Herein we show that the self-assembly of TiO2 nanoparticles (NP) functionalized with methyl viologen can be controlled both by light irradiation and chemical reduction through cucurbit[8]uril-enhanced radical cation dimerization interactions. Moreover, the controlled assembly and disassembly of this system are accompanied by switchable photocatalytic activity of the TiO2 NPs, which shows potential application as a novel smart and recyclable photocatalyst.
Co-reporter:Qi Zhang; Da-Hui Qu; Qiao-Chun Wang ; He Tian
Angewandte Chemie 2015 Volume 127( Issue 52) pp:16015-16019
Publication Date(Web):
DOI:10.1002/ange.201509071
Abstract
The realization of controllable multicomponent self-assembly through reversible supramolecular interactions is a challenging goal, and is an important strategy for the fabrication of switchable nanomaterials. Herein we show that the self-assembly of TiO2 nanoparticles (NP) functionalized with methyl viologen can be controlled both by light irradiation and chemical reduction through cucurbit[8]uril-enhanced radical cation dimerization interactions. Moreover, the controlled assembly and disassembly of this system are accompanied by switchable photocatalytic activity of the TiO2 NPs, which shows potential application as a novel smart and recyclable photocatalyst.
Co-reporter:Qian-Fu Luo, Lan Zhu, Si-Jia Rao, Hong Li, Qi Miao, and Da-Hui Qu
The Journal of Organic Chemistry 2015 Volume 80(Issue 9) pp:4704-4709
Publication Date(Web):April 15, 2015
DOI:10.1021/acs.joc.5b00627
Heterorotaxanes have been emerging as an important class of mechanically interlocked molecules and have attracted much attention in recent years. Driven by the distinguishable host–guest interactions between crown ether macrocycles and ammonium with different sizes, a novel hetero[4]rotaxane was successfully prepared by employing the combination of copper-catalyzed “click” reaction and P(n-Bu)3-catalyzed esterification reaction as stoppering reactions. The hetero[4]rotaxane contains an interlocked species in which a dibenzo[24]crown-8 ring threaded by a dibenzylammonium-containing component with two benzo[21]crown-7 macrocycles at both ends to act as stoppers, and each of the two benzo[21]crown-7 rings is also threaded with a benzylalkylammonium unit to form the second interlocked species. The hetero[4]rotaxane was prepared through two different stepwise synthetic routes, and the complicated chemical structure of the hetero[4]rotaxane was well-characterized by 1H NMR spectroscopy and high-resolution electrospray ionization (HR-ESI) mass spectrometry. The investigation shows that the construction of complicated topological heterorotaxane can be achieved via distinct approaches with high efficiencies, which may provide a foundation for the construction of more sophisticated heterorotaxane systems or functional supermolecules.
Co-reporter:Hong Li
Science China Chemistry 2015 Volume 58( Issue 6) pp:916-921
Publication Date(Web):2015 June
DOI:10.1007/s11426-015-5417-7
Molecular switches that can undergo reversible switching between two or more different states in response to external stimuli have been used in the fabrication of various optoelectronic devices and smart materials for many decades, and also found many applications in sensing, molecular self-assembly and photo-controlled biological systems. Recently, mechanically interlocked molecules, such as rotaxanes and catenanes, and molecular rotary motors based on overcrowded alkenes have emerged as two new kinds of molecular switches. Some novel applications of above-mentioned molecular switches have been discovered. In this mini review, we mainly highlight noticeable achievements over the past decade in this field, and summarize the applications of new types of molecular switches, for instance, controlling the chiral space to regulate catalytic reaction as organocatalysts, controlling molecular motions, synthesizing a peptide in a sequence-specific manner and modulating the wettability of the self-assembled monolayers.
Co-reporter:Hong Li, Xin Li, Hans Ågren, and Da-Hui Qu
Organic Letters 2014 Volume 16(Issue 18) pp:4940-4943
Publication Date(Web):September 10, 2014
DOI:10.1021/ol502466x
Two novel star-shaped [1](n)rotaxanes with three and four identical [1]rotaxane arms but different multibranched cores were designed, synthesized, and well-characterized. In the two systems, external base−acid stimuli result in the uniform relative mechanical movement of the macrocyclic rings and threads of their [1]rotaxane arms. The energy-minimized structures of the two rotaxanes in different states were obtained using molecular dynamics simulations in acetone solution, suggesting the construction of more sophisticated molecular machines mimicking the extension and contraction motions.
Co-reporter:Hong Li, Xin Li, Zhan-Qi Cao, Da-Hui Qu, Hans Ågren, and He Tian
ACS Applied Materials & Interfaces 2014 Volume 6(Issue 21) pp:18921
Publication Date(Web):October 10, 2014
DOI:10.1021/am506283g
A multifunctional bis-branched [1]rotaxane containing a perylene bisimide (PBI) core and two identical bistable[1]rotaxane arms terminated with ferrocene units was prepared and characterized by 1H NMR, 13C NMR, and 2D ROESY NMR spectroscopies and by HR-ESI spectrometry. The system is shown to possess several key features: (1) In acetone solution, external acid–base stimuli can result in relative mechanical movements of its ring and thread, which can induce extension and contraction movements of the whole system accompanied by a rotational movement of the ferrocene units, thus realizing dual-mode molecular motions, and the optimized conformations at different states are obtained through molecular dynamics simulations employing the general Amber force field. (2) The introduction of PBI enables the system fluorescence encoding through distance-dependent photoinduced electron transfer process from the ferrocene units to the PBI fluorophore. (3) The addition of Zn2+ can increase the degree of aggregation of the system, while adding base hinders aggregation because of the movement of the macrocycle. The tunable aggregated nanostructural morphologies of [1]rotaxane were examined by scanning electron microscopy. These results can pave the way to achieve precise control of integrated and coupling nanomechanical motions at a single-molecule level and provide more insight into controlling the aggregate behavior of switchable mechanically interlocked molecules.Keywords: bistable rotaxanes; dual-mode motions; fluorescence; perylene bisimide; tunable aggregation
Co-reporter:Xin Fu, Qiwei Zhang, Gang Wu, Wei Zhou, Qiao-Chun Wang and Da-Hui Qu
Polymer Chemistry 2014 vol. 5(Issue 23) pp:6662-6666
Publication Date(Web):14 Aug 2014
DOI:10.1039/C4PY00894D
A fluorescent hyperbranched supramolecular polymer was constructed through triple hydrogen bonding interactions between a three-arm monomer (PTDA) which possesses one melamine moiety in each arm and a perylene bisimide derivative (PBI 1) in dichloromethane.
Co-reporter:Wei Zhou, Ying Wu, Bao-Qi Zhai, Qiao-Chun Wang and Da-Hui Qu
RSC Advances 2014 vol. 4(Issue 10) pp:5148-5151
Publication Date(Web):12 Dec 2013
DOI:10.1039/C3RA46517A
We report an anthracene-containing bistable [2]rotaxane that can respond to the acidic/basic reagents, the change of the solvent polarity, and the counteranions, etc. The movement can generate remarkable, high-contrast fluorescent intensity change, along with an obvious color change.
Co-reporter:Shi-Lin Yu, Xiao-Qiu Dou, Da-Hui Qu, Chuan-Liang Feng
Journal of Molecular Liquids 2014 190() pp: 94-98
Publication Date(Web):
DOI:10.1016/j.molliq.2013.10.031
Co-reporter:Hong Li, Xin Li, Ying Wu, Hans Ågren, and Da-Hui Qu
The Journal of Organic Chemistry 2014 Volume 79(Issue 15) pp:6996-7004
Publication Date(Web):July 16, 2014
DOI:10.1021/jo501127h
A novel bistable symmetric [2](2)rotaxane was prepared by a threading-followed-by-stoppering strategy and characterized with 1H, 13C, and 2D ROESY NMR spectroscopy and HR-ESI spectrometry. The symmetric [2](2)rotaxane system consists of an anthracene-based bis(crown ether) as macrocycles, and each of the two dibenzo[24]crown-8 (DB24C8) rings is threaded by the pendant substituents of a symmetrically substituted central rotatable ferrocene subunit that possesses two distinguishable recognition sites for the DB24C8 ring: namely, a dibenzylammonium site and an N-methyltriazolium site. The uniform shuttling motion of the thread relative to the two DB24C8 rings in [2](2)rotaxane can be driven by external acid–base stimuli, which was evidenced by 1H and 2D ROESY NMR spectroscopy. Furthermore, molecular dynamics simulations of the [2](2)rotaxane were carried out both in protonated (stretched) and in neutral (contracted) forms. The calculated percentage change in molecular length of the [2](2)rotaxane between the two end-capping bis(methoxyl)phenyl groups is about 48% in the two different states (in acetone), which is much larger than the percentage change (∼27%) in human muscle. Moreover, in the two states, the C*–Cp–Cp–C* dihedral angles are computed as −177° in the stretched state and −112° in the contracted state, indicating a correlation between the translational and rotational motions of the [2](2)rotaxane.
Co-reporter:Jian Yao;Hong Li;Ya-Nan Xu;Dr. Qiao-Chun Wang ;Dr. Da-Hui Qu
Chemistry – An Asian Journal 2014 Volume 9( Issue 12) pp:3482-3490
Publication Date(Web):
DOI:10.1002/asia.201402789
Abstract
A bis-branched [3]rotaxane, with two [2]rotaxane arms separated by an oligo(para-phenylenevinylene) (OPV) fluorophore, was designed and investigated. Each [2]rotaxane arm employed a difluoroboradiaza-s-indacene (BODIPY) dye-functionalized dibenzo[24]crown-8 macrocycle interlocked onto a dibenzylammonium in the rod part. The chemical structure of the [3]rotaxane was confirmed and characterized by 1H and 13C NMR spectroscopy and high-resolution ESI mass spectrometry. The photophysical properties of [3]rotaxane and its reference systems were investigated through UV/Vis absorption, fluorescence, and time-resolved fluorescence spectroscopy. An efficient energy-transfer process in [3]rotaxane occurred from the OPV donor to the BODIPY acceptor because of the large overlap between the absorption spectrum of the BODIPY moiety and the emission spectrum of the OPV fluorophore; this shows the important potential of this system for designing functional molecular systems.
Co-reporter:Hui Zhang, Qiang Liu, Jing Li, and Da-Hui Qu
Organic Letters 2013 Volume 15(Issue 2) pp:338-341
Publication Date(Web):January 7, 2013
DOI:10.1021/ol3032686
A novel star-shaped zinc porphyrin cored [5]rotaxane with four rotaxane arms was synthesized and well characterized by 1H, 13C NMR spectroscopy and HR-ESI mass spectrometry. The introduction of the zinc porphyrin core enabled the [5]rotaxane to have a fixed shape and symmetrical structure, and the simultaneous shuttling motion of four macrocycles can be driven by external acid–base stimuli. This kind of topological structure exhibits important potential in the design and construction of large sophisticated assemblies.
Co-reporter:Hong Li, Ji-Na Zhang, Wei Zhou, Hui Zhang, Qiong Zhang, Da-Hui Qu, and He Tian
Organic Letters 2013 Volume 15(Issue 12) pp:3070-3073
Publication Date(Web):June 7, 2013
DOI:10.1021/ol401251u
We report the operation of a ferrocene-based bistable [1]rotaxane that can work in two parallel platforms. In an “active” signal mode, the relative mechanical movement of its ring and thread in response to external acid–base-stimuli can result in a remarkable fluorescence signal output observed by the naked eye, whereas no obvious fluorescence change occurred in a “silent” signal mode after oxidation. Its fluorescence responses to the different combinations of DBU and/or Fe(ClO4)3 corresponds to an INHIBIT logic gate.
Co-reporter:Hui Zhang, Bin Zhou, Hong Li, Da-Hui Qu, and He Tian
The Journal of Organic Chemistry 2013 Volume 78(Issue 5) pp:2091-2098
Publication Date(Web):October 29, 2012
DOI:10.1021/jo302107a
In the past few decades, bistable [2]rotaxanes have been extensively studied because of their applications in the fields of functional molecules and molecular machines. In this paper, a di-ferrocene-functionalized [2]rotaxane with two fluorophores as stoppers was designed, prepared, and studied. In this bistable [2]rotaxane, a dibenzo-24-crown-8 macrocycle functionalized with two ferrocene moieties as electron donors can reversibly shuttle between two distinct stations, namely, a dialkylammonium recognition site and a N-methyltriazolium recognition site, by external acid–base stimuli, which has been demonstrated using 1H NMR spectroscopy. It has been shown that, by introducing two ferrocene units into the macrocycle component, the fluorescence of two fluorescent stoppers, namely, the anthracene fluorophore and the 4-morpholin-naphthalimide fluorophore, can be changed in an alternate mode by an adjustable, distance-dependent photoinduced electron transfer process that occurs between the ferrocene electron donors and each of the two fluorophores.
Co-reporter:Ji-Na Zhang;Hong Li;Wei Zhou;Shi-Lin Yu;Dr. Da-Hui Qu;Dr. He Tian
Chemistry - A European Journal 2013 Volume 19( Issue 50) pp:17192-17200
Publication Date(Web):
DOI:10.1002/chem.201303026
Abstract
Two novel tribranched [4]rotaxanes with a 1,3,5-triphenylene core and three rotaxane arms have been designed, synthesized, and characterized by 1H and 13C NMR spectroscopies and HR-ESI mass spectrometry. [4]Rotaxanes 1 and 2 each possess the same three-armed skeleton. Each arm incorporates two distinguishable binding sites for a dibenzo[24]crown-8 ring, namely a dibenzylammonium site and an N-methyltriazolium site, and is terminated by a 4-morpholino-naphthalimide fluorophore as a stopper. [4]Rotaxane 1 has three di-ferrocene-functionalized dibenzo[24]crown-8 rings whereas 2 has three simple dibenzo[24]crown-8 rings interlocked with the thread component. Uniform shuttling motions of the three macrocycles in both 1 and 2 can be driven by external acid–base stimuli, which were confirmed by 1H NMR spectroscopy. However, [4]rotaxanes 1 and 2 show distinct modes of fluorescence modulation in response to external acid–base stimuli. [4]Rotaxane 1 exhibits a remarkable fluorescence decrease in response to the addition of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as a base, which can displace the ferrocene-functionalized macrocycle from the dibenzylammonium station to the N-methyltriazolium station. In contrast, the fluorescence intensity of [4]rotaxane 2 showed an enhancement with the addition of DBU. Time-resolved fluorescence measurements have been performed. The different photoinduced electron-transfer processes responsible for the fluorescence changes in the two molecular systems are discussed. Topological structures of this kind have significant potential for the design and construction of large and complex assemblies with controllable functions.
Co-reporter:Wei Zhou, Hui Zhang, Hong Li, Yu Zhang, Qiao-Chun Wang, Da-Hui Qu
Tetrahedron 2013 69(26) pp: 5319-5325
Publication Date(Web):
DOI:10.1016/j.tet.2013.04.119
Co-reporter:Wei Zhou, Ya-Jing Guo, and Da-Hui Qu
The Journal of Organic Chemistry 2013 Volume 78(Issue 2) pp:590-596
Publication Date(Web):December 18, 2012
DOI:10.1021/jo302426c
A [3]rotaxane with two [2]rotaxane arms bridged by an overcrowded alkene switch has been constructed to perform the clamlike motion in response to light stimulus. We demonstrated that this [3]rotaxane can undergo reversible conformational changes caused by the trans–cis isomerizations of the central double bond with a favorable photostationary state (up to 90% conversion). It has been shown that the clamlike motion causes remarkable UV–vis and fluorescence spectral changes, allowing it to behave as a reversible optical molecular switch.
Co-reporter:Qiwei Zhang, Da-Hui Qu, Junchen Wu, Xiang Ma, Qiaochun Wang, and He Tian
Langmuir 2013 Volume 29(Issue 17) pp:5345-5350
Publication Date(Web):April 6, 2013
DOI:10.1021/la4012444
Covalent or noncovalent linked polymers with stimuli-responsive properties have been well researched as a kind of advanced functional materials. However, little effort has been devoted to establishing a bridge for switching between covalent polymers and noncovalent polymers. Actually, such unitive system is promising because it can combine their chemical advantages of two types of polymers in a single and tunable platform. Herein, by taking advantage of reversible photodimerization of coumarins and host–guest assemblies with γ-cyclodextrin (γ-CD), we demonstrate a simple and effective way to construct a dual-modality supramolecular polymer, which can be switched between a noncovalent polymer and its corresponding covalent polymer in response to light stimuli. Moreover, this unique switchable polymer can also be employed to construct a dual-stimuli responsive supramolecular hydrogel with the surfactant cetyl trimethylammonium bromide (CTAB). This methodology establishes a bridge between the two “polymer mansions” and is promising to open a new class of photoswitchable materials.
Co-reporter:Hong Li, Hui Zhang, Qiong Zhang, Qi-Wei Zhang, and Da-Hui Qu
Organic Letters 2012 Volume 14(Issue 23) pp:5900-5903
Publication Date(Web):November 12, 2012
DOI:10.1021/ol302826g
A [1]rotaxane, in which a linear rod is attached to one cyclopentadienyl (Cp) ring of a ferrocene unit and threaded into a dibenzo-24-crown-8 connected to the other Cp ring, was prepared. The mechanical motion of the rod-like part relative to the macrocycle has been demonstrated using 1H NMR spectroscopy. Cyclic voltammetry (CV) showed that the system can be chemically switched between electrochemically reversible and irreversible states, depending on the inclusion and exclusion of the ammonium/amine group from the macrocycle.
Co-reporter:Hui Zhang, Juan Hu, and Da-Hui Qu
Organic Letters 2012 Volume 14(Issue 9) pp:2334-2337
Publication Date(Web):April 19, 2012
DOI:10.1021/ol300753d
The shuttling motion of the ferrocene-functionalized macrocycle between the dibenzylammonium and the N-methyltriazolium recognition sites in a bistable [2]rotaxane, as well as the photoinduced electron transfer process occurring between ferrocene units and the morpholin-naphthalimide fluorescent stopper, can be adjusted not only by acid–base stimuli but also addition–removal of the fluoride anion, along with remarkable, high-contrast fluorescent intensity changes.
Co-reporter:Yi Qu, Sanyin Qu, Lin Yang, Jianli Hua, Dahui Qu
Sensors and Actuators B: Chemical 2012 173() pp: 225-233
Publication Date(Web):
DOI:10.1016/j.snb.2012.06.093
Co-reporter:Hui Zhang, Xin-Xin Kou, Qiong Zhang, Da-Hui Qu and He Tian
Organic & Biomolecular Chemistry 2011 vol. 9(Issue 11) pp:4051-4056
Publication Date(Web):16 Mar 2011
DOI:10.1039/C1OB05307H
Rotaxanes have attracted much attention because of their challenging constructions and potential applications. In this paper, a multi-state [2]rotaxane, in which a dithienylethene-functionalized dibenzo-24-crown-8 macrocycle was interlocked onto a thread component bearing a 4-morpholin-naphthalimide fluorescent stopper and two distinct recognition sites, namely, dibenzylammonium and N-methyltriazolium recognition sites, was prepared and studied. By introducing a dithienylethene photochrome into the macrocycle component, multi-mode alteration of the intercomponent interactions, such as energy transfer, electron transfer, and charge transfer interaction between the photochrome and the fluorescent naphthalimide stopper could be altered in this multi-state rotaxane system in response to the combination of chemical and photochemical stimuli.
Co-reporter:Hui Zhang, Xin-Xin Kou, Qiong Zhang, Da-Hui Qu and He Tian
Organic & Biomolecular Chemistry 2011 - vol. 9(Issue 11) pp:NaN4056-4056
Publication Date(Web):2011/03/16
DOI:10.1039/C1OB05307H
Rotaxanes have attracted much attention because of their challenging constructions and potential applications. In this paper, a multi-state [2]rotaxane, in which a dithienylethene-functionalized dibenzo-24-crown-8 macrocycle was interlocked onto a thread component bearing a 4-morpholin-naphthalimide fluorescent stopper and two distinct recognition sites, namely, dibenzylammonium and N-methyltriazolium recognition sites, was prepared and studied. By introducing a dithienylethene photochrome into the macrocycle component, multi-mode alteration of the intercomponent interactions, such as energy transfer, electron transfer, and charge transfer interaction between the photochrome and the fluorescent naphthalimide stopper could be altered in this multi-state rotaxane system in response to the combination of chemical and photochemical stimuli.
Co-reporter:Jing-Jing Yu, Zhan-Qi Cao, Qi Zhang, Shun Yang, Da-Hui Qu and He Tian
Chemical Communications 2016 - vol. 52(Issue 81) pp:NaN12059-12059
Publication Date(Web):2016/09/09
DOI:10.1039/C6CC06458B
A novel photo-responsive nano-container was successfully constructed based on well-defined vesicles formed by an amphiphilic overcrowded alkene switch. The nano-container could adjust its inner volume in reversible photo/heat controlled mode, which could show potential in remote drug delivery systems.
Co-reporter:Xin Fu, Qi Zhang, Si-Jia Rao, Da-Hui Qu and He Tian
Chemical Science (2010-Present) 2016 - vol. 7(Issue 3) pp:NaN1701-1701
Publication Date(Web):2016/01/12
DOI:10.1039/C5SC04844C
The construction and efficient synthesis of hetero[n]rotaxanes with high structural complexity are always attractive challenges. Herein, we demonstrate a facile one-pot preparation of a hetero[4]rotaxane, by employing a self-sorting strategy, which contains an interpenetrated dibenzo-24-crown-8 (DB24C8) based [c2]daisy chain structure and is ended with a benzo-21-crown-7 (B21C7) based rotaxane at each side. The key to the design involved encoding the selective threading using a steric hindrance-related “language”, where highly selective self-assemblies occurred in a three-component self-sorting process, which included the threading of a benzylalkylammonium into a B21C7 and interpenetrated dimerized formation of a DB24C8 based [c2]daisy chain simultaneously; the precise pre-assembled system resulted in the efficient synthesis of hetero[4]rotaxane with a high-level of structural complexity under the “CuAAC” reaction.
Co-reporter:Ruirui Gu, Jian Yao, Xin Fu, Wei Zhou and Da-Hui Qu
Chemical Communications 2015 - vol. 51(Issue 25) pp:NaN5431-5431
Publication Date(Web):2014/11/18
DOI:10.1039/C4CC08533G
A hyperbranched supramolecular polymer has been constructed through orthogonal self-crosslinking by two classical binding interactions: triple hydrogen bonding interaction between a three-arm melamine derivative and DB24C8-containing bisimide and host–guest interaction between DB24C8 crown ether and ditopic dibenzyl ammonium moieties.
Co-reporter:Zhan-Qi Cao, Qi Miao, Qi Zhang, Hong Li, Da-Hui Qu and He Tian
Chemical Communications 2015 - vol. 51(Issue 24) pp:NaN4976-4976
Publication Date(Web):2015/01/12
DOI:10.1039/C4CC09976A
A fluorescent bistable [2]rotaxane terminated with an alkyne functional group was constructed and immobilized onto the surface of SiO2 nanoparticles through click reaction. The shuttling motion of the macrocycle component between two different stations was driven by external acid–base stimuli both in solution and on SiO2 nanoparticles, accompanied by visual fluorescence changes.
Co-reporter:Zhan-Qi Cao, Yi-Chuan Wang, Ai-Hua Zou, Gábor London, Qi Zhang, Chuan Gao and Da-Hui Qu
Chemical Communications 2017 - vol. 53(Issue 62) pp:NaN8686-8686
Publication Date(Web):2017/07/11
DOI:10.1039/C7CC05008A
An acid/base responsive amphiphilic [2]rotaxane switch containing a hydrophilic macrocycle component and a hydrophobic terminal bulky group was prepared and characterized. The morphology of the supramolecular assemblies formed by the rotaxanes could be switched between spherical vesicles and worm-like micelles using acid/base stimuli, as confirmed by transmission electron microscopy (TEM).
![Dibenzo[n,n']anthra[2,3-b:6,7-b']bis[1,4,7,10,13,16,19,22]octaoxacyclotetracosin, 6,7,9,10,12,13,19,20,22,23,25,26,33,34,36,37,39,40,46,47,49,50,52,53-tetracosahydro-16,43-dipropyl-](/data/chemimg/3727600/1197881-09-6.png)
![Dibenzo[n,n']anthra[2,3-b:6,7-b']bis[1,4,7,10,13,16,19,22]octaoxacyclotetracosin, 6,7,9,10,12,13,19,20,22,23,25,26,33,34,36,37,39,40,46,47,49,50,52,53-tetracosahydro-16,43-dipropyl-](/data/chemimg/3727600/1197881-09-6_b.png)
![Pentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23-dodecaene-25,26,27-triol, 28,28'-[1,2-ethanediylbis(oxy)]bis-](/data/chemimg/103400/950585-95-2.png)
![Pentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23-dodecaene-25,26,27-triol, 28,28'-[1,2-ethanediylbis(oxy)]bis-](/data/chemimg/103400/950585-95-2_b.png)
![1-Decanol, 10-[4-(aminomethyl)phenoxy]-](/data/chemimg/3726800/1241376-73-7.png)
![1-Decanol, 10-[4-(aminomethyl)phenoxy]-](/data/chemimg/3726800/1241376-73-7_b.png)
![UREA, N-BUTYL-N'-[6-(1-ETHYLPENTYL)-1,4-DIHYDRO-4-OXO-2-PYRIMIDINYL]-](http://img.cochemist.com/ccimg/745900/745822-21-3.png)
![UREA, N-BUTYL-N'-[6-(1-ETHYLPENTYL)-1,4-DIHYDRO-4-OXO-2-PYRIMIDINYL]-](http://img.cochemist.com/ccimg/745900/745822-21-3_b.png)
![Anthra[2,1,9-def:6,5,10-d'e'f']diisoquinoline-1,3,8,10(2H,9H)-tetrone, 2-butyl-5,6,12,13-tetrakis[4-(1,1-dimethylethyl)phenoxy]-](/data/chemimg/134800/724422-60-0.png)
![Anthra[2,1,9-def:6,5,10-d'e'f']diisoquinoline-1,3,8,10(2H,9H)-tetrone, 2-butyl-5,6,12,13-tetrakis[4-(1,1-dimethylethyl)phenoxy]-](/data/chemimg/134800/724422-60-0_b.png)
![1H-Imidazole-1-carboxamide,N-[6-(1-ethylpentyl)-1,4-dihydro-4-oxo-2-pyrimidinyl]-](http://img.cochemist.com/ccimg/522700/522647-64-9.png)
![1H-Imidazole-1-carboxamide,N-[6-(1-ethylpentyl)-1,4-dihydro-4-oxo-2-pyrimidinyl]-](http://img.cochemist.com/ccimg/522700/522647-64-9_b.png)
![Dibenz[b,n][1,4,7,10,13,16,19,22]octaoxacyclotetracosin-2,3-dicarbonitrile, 6,7,9,10,12,13,20,21,23,24,26,27-dodecahydro-](/data/chemimg/3724100/268566-97-8.png)
![Dibenz[b,n][1,4,7,10,13,16,19,22]octaoxacyclotetracosin-2,3-dicarbonitrile, 6,7,9,10,12,13,20,21,23,24,26,27-dodecahydro-](/data/chemimg/3724100/268566-97-8_b.png)
![Dibenz[b,n][1,4,7,10,13,16,19,22]octaoxacyclotetracosin-2-carboxylic acid, 6,7,9,10,12,13,20,21,23,24,26,27-dodecahydro-](/data/chemimg/103300/215322-83-1.png)
![Dibenz[b,n][1,4,7,10,13,16,19,22]octaoxacyclotetracosin-2-carboxylic acid, 6,7,9,10,12,13,20,21,23,24,26,27-dodecahydro-](/data/chemimg/103300/215322-83-1_b.png)
![Benzenemethanamine, 4-[2-(2-propyn-1-yloxy)ethoxy]-](/data/chemimg/3723500/1412334-19-0.png)
![Benzenemethanamine, 4-[2-(2-propyn-1-yloxy)ethoxy]-](/data/chemimg/3723500/1412334-19-0_b.png)
![Ferrocene, 1,1''-[(6,7,9,10,12,13,20,21,23,24,26,27-dodecahydrodibenz[b,n][1,4,7,10,13,16,19,22]octaoxacyclotetracosin-2,17-diyl)bis(methyleneoxycarbonyl)]bis-](/data/chemimg/3727600/1373558-10-1.png)
![Ferrocene, 1,1''-[(6,7,9,10,12,13,20,21,23,24,26,27-dodecahydrodibenz[b,n][1,4,7,10,13,16,19,22]octaoxacyclotetracosin-2,17-diyl)bis(methyleneoxycarbonyl)]bis-](/data/chemimg/3727600/1373558-10-1_b.png)
![Dibenz[b,n][1,4,7,10,13,16,19,22]octaoxacyclotetracosin-2-carboxaldehyde, 6,7,9,10,12,13,20,21,23,24,26,27-dodecahydro-](/data/chemimg/103300/209855-90-3.png)
![Dibenz[b,n][1,4,7,10,13,16,19,22]octaoxacyclotetracosin-2-carboxaldehyde, 6,7,9,10,12,13,20,21,23,24,26,27-dodecahydro-](/data/chemimg/103300/209855-90-3_b.png)
