Synthesis and characterization of bis-[1]rotaxanes via salen-bridged bis-pillar[5]arenes

The series of salen-bridged bis-pillar[1]arenes were conveniently prepared by condensation reaction of5,5'-methylenebis(2-hydroxybenzalde hyde)or 5,5'-(propane-2,2-diyl)bis(2-hydroxybenzaldehyde)with mono-amido-functionalized pillar[5]arenes containing different terminal aminoalkyl groups in refluxing ethanol.The^1H NMR and 2D-NOESY spectra indicated that the salen-bridged bis-pillar[5]arenes with longer allcylene linker(n=3,4,6)formed the fascinating bis-[1]rotaxanes,while the salenbridged bis-pillar[5]arenes with short hydrazine and ethylenediamino linker(n=0,2)predominately existed in free form.The single crystal structure of the bis-pillar[5]are ne ambiguously indicated that two propylenediamino linker inserted in to two cavities of pillar[5]arene to form a novel bis-[1]rotaxanes.     

Preparation of two new [2]rotaxanes based on the pillar[5]arene/alkane recognition motif

Based on the pillar[5]arene/alkane recognition motif, two [2]rotaxanes were successfully prepared. Their formation was confirmed by NMR spectroscopy and ESI mass spectrometry. We also demonstrated that 3,5-dinitrophenyl group and 3,5-bis(trifluoromethyl)phenyl group are big enough to work as stoppers for DPPillar[5]arene, which lays a foundation for the preparation of more complex and functional supramolecular structures.     

Diversity Oriented Preparation of Pillar[5]arene-Containing [2]Rotaxanes by a Stopper Exchange Strategy

Rotaxane building blocks bearing 3,5-bis(trifluoromethyl) benzenesulfonate (BTBS) stoppers have been efficiently prepared from a pillar[5]arene derivative, 3,5-bis(trifluoromethyl) benzenesulfonyl chloride (BTBSCl) and different diols, namely 1,10-decanediol and 1,12-dodecanediol. The BTBS moieties of these compounds are good leaving groups and stopper exchange reactions could be achieved by treatment with different nucleophiles thus affording rotaxanes with ester, thioether or ether stoppers.     

Construction and investigation of photo-switch property of azobenzene-bridged pillar[5]arene-based [3]rotaxanes

Series of azobenzene-bridged pillar[5]arene-based [3]rotaxanes with different alkyl chain length of guest molecules were constructed by threading-endcapping method with alkylenetriazole as axile and tetrahydrochromene as endcapping group.The encapsulation of pillar[5]arenes were proved by highresolution mass,¹ H NMR and NOESY spectra.The photo-responsive property were examined by irradiation of the synthesized [3]rotaxanes with 365 nm and blue light LED,which caused trans to cis and cis to trans isomerization,respectively.Irradiation of corresponding model guest compounds without pillar[5]arene encapsulation resulted in near completely trans to cis and cis to trans isomerization,indicating the existence of pillar[5]arenes is the determining factor for the comprised photo isomerization efficiency.     

Construction of [1]rotaxanes with pillar[5]arene as the wheel and terpyridine as the stopper

The condensation reaction ofω-aminoalkyleneamide-functionalized pillar[5]arenes with 2-(4-([2,2’:6’,2〃-terpyridin]-4’-yl)phenoxy)acetic acid or 4-(4-([2,2’:6’,2"-terpyridin]-4’-yl)phenoxy)butanoic acid in dry chloroform at room temperature under the catalysis of HOBT/EDCl resulted in novel pillar[5]arene diamido-bridged terpyridine derivatives.~1 H NMR and 2 D NOESY spectra clearly indicated that the interesting[1]rotaxanes were formed by longer alkylene such as propylene,butylene and hexylenediamido chains threading into the cavity of the pillar[5]arene and with larger terpyridine acting as the stopper.However,the shorter ethylenediamido chain only exists outer of cavity of pillar[5]arene and the molecule exist on free form.     

Pillar[5]arene decaamine: synthesis, encapsulation of very long linear diacids and formation of ion pair-stopped [2]rotaxanes

A pillar[5]arene decaamine has been synthesized and revealed to encapsulate linear diacids in neutral, alkaline, and acidic conditions, driven by the hydrophobic and electrostatic interactions, to give rise to pseudo[2]rotaxanes. Ion pair-bonded stoppers can further lock the diacids to generate stable water soluble [2]rotaxanes.     

Pentafluorophenyl Esters as Exchangeable Stoppers for the Construction of Photoactive [2]Rotaxanes

Stable pillar[5]arene-containing [2]rotaxane building blocks with pentafluorophenyl ester stoppers have been efficiently prepared on a multi-gram scale. Reaction of these building blocks with various nucleophiles gave access to a wide range of [2]rotaxanes with amide, ester or thioester stoppers in good to excellent yields. The rotaxane structure is fully preserved during these chemical transformations. Actually, the addition-elimination mechanism at work during these transformations totally prevents the unthreading of the axle moiety of the mechanically interlocked system. The stopper exchange reactions were optimized both in solution and under mechanochemical solvent-free conditions. While amide formation is more efficient in solution, the solvent-free conditions are more powerful for the transesterification reactions. Starting from a fullerene-functionalized pillar[5]arene derivative, this new strategy gave easy access to a photoactive [2]rotaxane incorporating a C₆₀ moiety and two Bodipy stoppers. Despite the absence of covalent connectivity between the Bodipy and the fullerene moieties in this photoactive molecular device, efficient through-space excited state interactions have been evidenced in this rotaxane.     

Synthesis and characterization of a new pillar[5]arene-based [1]rotaxane

In this study, we reported the synthesis of three kinds of mono-functional pillar[5]arene derivatives PRI, PRII and R and their structures were studied by 1D and 2D NMR spectra and mass spectra. The 2D NMR spectra including ¹H-¹³C HSQC, ¹H-¹H COSY and NOESY spectra indicated that PRI and PRII are both stable self-included pseudo[1]rotaxanes in CDCl₃. These original structures are promising compounds for the design of pillar[5]-based [1]rotaxane. And the results showed that R could exist stable in CDCl₃ and DMSO because of the coordination of N-H?O hydrogen bonding interaction and C-H?π interaction.     

Helic[6]arene-Based Chiral Pseudo[1]rotaxanes and [1]Rotaxanes

Chiral pseudo[1]rotaxanes and [1]rotaxanes constructed from macrocyclic arenes still remain a big challenge mainly owing to the lack of such chiral macrocycles. In this work, a new system of chiral pseudo[1]rotaxanes formed by self-inclusion of helic[6]arene containing amide linked with the terminal tertiary amines was first discovered. Based on an atom-economic stopping strategy, a pair of chiral [1]rotaxanes were conveniently obtained in almost quantitative yields by blocking the pseudo[1]rotaxanes with monobenzyl bromide of tetraphenylethene. The structures of pseudo[1]rotaxanes and [1]rotaxanes were characterized by 2D NMR spectra in solution, combined with DFT calculations. The photophysical properties further revealed the efficient chirality transfer of helic[6]arene to the tetraphenylethene moiety, compared to their unthreaded chiral isomers. The discovery of the chiral pseudo[1]rotaxanes allows for a wide and available synthesis of chiral [1]rotaxanes, and also opening a new avenue to the design of chiral supramolecular materials.     

Langmuir and Langmuir–Blodgett Films from Amphiphilic Pillar[5]arene‐Containing [2]Rotaxanes

Amphiphilic pillar[5]arene‐containing [2]rotaxanes have been prepared and fully characterized. In the particular case of the [2]rotaxane incorporating a 1,4‐diethoxypillar[5]arene subunit, the structure of the compound was confirmed by X‐ray crystal structure analysis. Owing to a good hydrophilic/hydrophobic balance, stable Langmuir films have been obtained for these rotaxanes and the size of the peripheral alkyl chains on the pillar[5]arene subunit has a dramatic influence on the reversibility during compression–decompression cycles. Indeed, when these are small enough, molecular reorganization of the rotaxane by gliding motions are capable of preventing strong π–π interactions between neighboring macrocycles in the thin film.     

High-yield diastereoselective synthesis of planar chiral [2]- and [3]rotaxanes constructed from per-ethylated pillar[5]arene and pyridinium derivatives

Planar chiral [2]- and [3]rotaxanes constructed from pillar[5]arenes as wheels and pyridinium derivatives as axles were obtained in high yield using click reactions. The process of rotaxane formation was diastereoselective; the obtained [2]rotaxane was a racemic mixture consisting of (pS, pS, pS, pS, pS) and (pR, pR, pR, pR, pR) forms of the per-ethylated pillar[5]arene (C2) wheel, and other possible types of the [2]rotaxane did not form. Isolation of the enantiopure [2]rotaxanes with one axle through (pS, pS, pS, pS, pS)-C2 or (pR, pR, pR, pR, pR)-C2 wheels was accomplished. Furthermore, pillar[5]arene-based [3]rotaxane was successfully synthesized by attachment of two pseudo [2]rotaxanes onto a bifunctional linker. [3]Rotaxane formed in a 1:2:1 mixture with one axle threaded through two (pS, pS, pS, pS, pS)-C2, one (pS, pS, pS, pS, pS)-C2 and one (pR, pR, pR, pR, pR)-C2 (meso form), or two (pR, pR, pR, pR, pR)-C2 wheels. The [3]rotaxane enantiomers and the meso form were successfully isolated using appropriate chiral HPLC column chromatography. The procedure developed in this study is the starting point for the creation of pillar[5]arene-based interlocked molecules.     

Post-assembly processing of [2]rotaxanes

The concept of using [2]rotaxanes that carry one or more surrogate stoppers which can subsequently be converted chemically into other structural units, resulting in the formation of new interlocked molecular compounds, is introduced and exemplified. Starting from simple NH2(+)-centered/crown-ether-based [2]rotaxanes, containing either one or two benzylic triphenylphosphonium stoppers, the well-known Wittig reaction has been employed to make, 1) other [2]rotaxanes, 2) higher order rotaxanes, 3) branched rotaxanes, and 4) molecular shuttles--all isolated as pure compounds, following catalytic hydrogenations of their carbon-carbon double bonds, obtained when aromatic aldehydes react with the ylides produced when the benzylic triphenylphosphonium derivatives are treated with strong base. The two starting [2]rotaxanes were characterized fully in solution and also in the solid state by X-ray crystallography. The new interlocked molecular compounds that result from carrying out post-assembly Wittig reactions on two [2]rotaxanes were characterized by (dynamic) 1H NMR spectroscopy. In the case of a molecular shuttle in which the crown ether component is dibenzo[24]-crown-8 (DB24C8), shuttling is slow on the 1H NMR timescale, even at high temperatures. However, when DB24C8 is replaced by benzometaphenylene[25]-crown-8 as the ring component in the molecular shuttle, the frequency of the shuttling is observed to be around 100 Hz in [D4]methanol at 63 degrees C.     

Novel [2]rotaxanes based on the recognition of pillar[5]arenes to an alkane functionalized with triazole moieties

Host-guest complexation between an alkane functionalized with triazole moieties and three pillar[5]arenes was studied. Three pillar[5]arene-based [2]rotaxanes were constructed based on this new recognition motif. The sequence of the yields of these [2]rotaxanes was consistent with the order of association constants between the three corresponding pillar[5]arenes and the alkane. ¹H NMR, electrospray ionization mass spectrometry, and NOESY NMR were employed to characterize these [2]rotaxanes.     

Synthesis of pillar[7]arene

The first synthesis of pillar[7]arene is reported with two methods.Method A:the FeCl₃-catalyzed condensation reaction of 1,4- dimethoxybenzene（1） with paraformaldehyde in CHCl₃ gave dimethoxypillar[7]arene（3）.Method B:the p-toluenesulfonic acid catalyzed condensation reaction of 2,5-bis（benzyloxymethyl）-1,4-dimethoxybenzene（2） in CH₂Cl₂ gave compound 3.Demethylation of 3 with BBr₃ gave pillar[7]arene（4）.The pillar[7]arene might be a perspective macrocyclic host in host-guest chemistry.     

Monofunctionalized pillar[5]arene-based stable [1]pseudorotaxane

A new monofunctionalized pillar[5]arene bearing imidazolium moiety that formed stable [1]pseudorotaxane even at high concentration (100 mmol/L) was reported. [1]Rotaxane was obtained effi ciently through thiol-ene reaction from [1]pseudorotaxane which further confi rmed the formation of [1]pseudorotaxane.     

Degenerate [2]rotaxanes with electrostatic barriers

A synthetic approach to the preparation of [2]rotaxanes (1-5·6PF(6)) incorporating bispyridinium derivatives and two 1,5-dioxynaphthalene (DNP) units situated in the rod portions of their dumbbell components that are encircled by a single cyclobis(paraquat-p-phenylene) tetracationic (CBPQT(4+)) ring has been developed. Since the π-electron-deficient bispyridinium units are introduced into the dumbbell components of the [2]rotaxanes 1-5·6PF(6), there are Coulombic charge-charge repulsions between these dicationic units and the CBPQT(4+) ring in the [2]rotaxanes. Thus, the CBPQT(4+) rings in the degenerate [2]rotaxanes exhibit slow shuttling between two DNP recognition sites on the (1)H NMR time-scale on account of the electrostatic barrier posed by the bispyridinium units, as demonstrated by variable-temperature (1)H NMR spectroscopy. Electrochemical experiments carried out on the [2]rotaxanes 1·6PF(6) and 2·6PF(6) indicate that the one-electron reduced bipyridinium radical cation in the dumbbell components of the [2]rotaxanes serves as an additional recognition site for the two-electron reduced CBPQT(2(˙+)) diradical cationic ring. Under appropriate conditions, the ring components in the degenerate rotaxanes 1·6PF(6) and 2·6PF(6) can shuttle along the recognition sites--two DNP units and one-electron reduced bipyridinium radical cation--under redox control.     

Pillar[5]arenes: fascinating cyclophanes with a bright future

Pillar[5]arenes are [1(5)]paracyclophane derivatives consisting of 1,4-disubstituted hydroquinones linked by methylene bridges in the 2,5-positions. The first report of these novel macrocycles was in 2008, when 1,4-dimethoxypillar[5]arene was prepared in 22% yield, and subsequent improvements in synthetic methods have allowed the number of derivatives to expand significantly. In addition to D(5) symmetric pillar[5]arenes, asymmetric pillar[5]arenes with two different substituents in the 1- and 4-positions and copillar[5]arenes consisting of two different repeat units in a 4 : 1 ratio have been synthesised. Crystallographic, computational and spectroscopic studies are starting to shed light on the compounds' unusual inclusion phenomena, from gelation and transportation of water through nanotubes to the formation of chromogenic rotaxanes. Applications as molecular sensors are starting to appear with a focus on guest detection by fluorescence quenching. This tutorial review will provide a summary of research into the pillar[5]arenes since their recent discovery.     

An Inorganic Click Reaction for the Synthesis of Interlocked Molecules

We describe the use of the cyaphide-azide 1,3-dipolar cycloaddition reaction for the synthesis of a new class of inorganic rotaxanes containing gold(I) triazaphosphole stoppers. Electron-deficient bis-azides, which thread perethylated pillar[5]arene in aromatic solvents, readily react with two equivalents of Au(IDipp)(CP) (IDipp=1,3-bis-(2,6-diisopropylphenyl)-imidazol-2-ylidene) to afford interlocked molecules via an inorganic click reaction. These transformations proceed in good yields (ca. 65 %) and in the absence of a catalyst. The resulting organometallic rotaxanes are air- and moisture-stable and can be purified by column chromatography under aerobic conditions. The targeted rotaxanes were characterized by multi-element nuclear magnetic resonance (NMR) spectroscopy, mass-spectrometry, and single-crystal X-ray diffraction.     

Construction of anion‐responsive crosslinked polypseudorotaxane based on molecular recognition of pillar[5]arene

A pillar[5]arene pendant polymer (Poly‐P[5]A) is synthesized via ROMP using Grubb's first‐generation catalyst. GPC analysis of the polymer suggested ~30 pendant pillar[5]arene units in the polymer. Supramolecular polypseudorotaxane assembly is constructed by intermolecularly crosslinking pendant pillar[5]arene units using a bispyridinium guest via host–guest complexation. Formation of the polypseudorotaxane assembly is characterized by 1D/2D NMR techniques and DLS analysis. Moreover, anion‐responsiveness of the polypseudorotaxane assembly is demonstrated by ¹H NMR spectroscopic analysis using chloride anion as external stimulus. Scanning electron microscopic analysis of the poly‐P[5]A showed breath‐figure assembly and upon crosslinking with G.2PF₆ the polymer self‐assemble to give a supramolecular polymer network. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1508–1515     

Self-assembly of novel [3]- and [2]rotaxanes based on donor-acceptor and hydrogen-bonding interactions. Intensified inter-ring repulsion interaction and shuttling behavior

Three novel hetero[3]rotaxanes, which comprise one neutral tetraamide cyclophane, one tetracationic cyclophane, and one linear component, have been assembled by utilizing hydrogen-bonding and donor-acceptor interactions, through three neutral [2]rotaxanes as intermediates. Three tetracationic [2]rotaxanes are also prepared for property comparison. For all three linear components, diamide subunits, the hydrogen-bonding templating moieties, are introduced at the center of the molecules, while the electron-rich hydrogquinone subunits, the donor-acceptor interaction templates, are incorporated between the diamides and the triphenylmethyl stoppers. Compared with the reported [3]rotaxanes, the novel hetero[3]rotaxanes exhibit remarkably intensified spatial interaction between the two ring components, which had been proved by (1)H NMR and UV study. For the first time, inter-ring NOEs are observed for interlocked [3]rotaxanes.