基于两亲性喹喔啉的超分子凝胶：手性信号反转以及多重响应手性光学开关

The regulation of supramolecular chirality has applications in various aspects including asymmetric catalysis, chiral sensing, optical materials and smart devices. Additionally, it provides opportunities for the simulation of important activities in living organisms and the clarification of their mechanisms. Herein, we synthesized a chiral gelator SQLG (styrylquinoxalinyl L-amino glutamic diamide) containing a π-conjugated headgroup by introducing the quinoxaline-derived moiety into L-glutamic diamide-based amphiphile via two simple condensation steps. SQLG self-assembled into nanofibers through multiple intermolecular interactions, including π–π stacking, hydrogen bonding and van der Waals interaction, leading to gelation of various organic solvents ranging from nonpolar to polar ones. Chirality transfer from the chiral center to the supramolecular level was observed when organogels formed, which manifested itself in circular dichroism (CD) spectra. The organogels formed in polar solvents such as N, N-dimethylformamide (DMF) and nonpolar solvents such as toluene exhibited opposite signals of supramolecular chirality, attributed to different hydrogen bonding strengths and thus two different types of gelator stacking modes of the gelators which was confirmed by infrared spectroscopy (IR) and X-ray diffraction (XRD). Circular polarized luminescence (CPL) denotes left-handed or right-handed circularly polarized light with different intensities emitted by the chiral luminescent system, and it characterizes the chirality of the excited state, which finds potential application in fields such as 3D optical displays, optical data storage, polarization-based information encryption and bioencoding. Owing to the strong fluorescence and supramolecular chirality, the toluene gel emitted right-handed circular polarized luminescence upon excitation, while the gel formed in DMF did not exhibit CPL emission because of its relatively weak fluorescence. Furthermore, the organogels responded rapidly and distinctly to the stimulus of acid due to the proton-accepting sites in the quinoxaline skeleton. Utilizing NMR spectroscopy, we found that the two nitrogen atoms in the quinoxaline moiety could be protonated upon acidification. During the process, intramolecular charge transfer (ICT) was significantly strengthened and the driving forces of self-assembly underwent remarkable changes, resulting in the collapse of the yellow transparent organogel into a red dispersion. Meanwhile, transformation from nanofibers to nanospheres was observed using a scanning electron microscope (SEM). With change in stacking modes in the supramolecular assembly, a complete inversion of the CD signal was detected. The CPL signal was found to be switched off, which along with the other changes of the system could subsequently be recovered by neutralization of the entire system. Therefore, we constructed a chiroptical switch with multiple stimuli-responsiveness through the introduction of an acid-sensitive π-conjugated moiety into the L-glutamic diamide-based chiral amphiphile.     

Phosphorus-based functional groups as hydrogen bonding templates for rotaxane formation

We report on the use of the hydrogen bond acceptor properties of some phosphorus-containing functional groups for the assembly of a series of [2]rotaxanes. Phosphinamides, and the homologous thio- and selenophosphinamides, act as hydrogen bond acceptors that, in conjunction with an appropriately positioned amide group on the thread, direct the assembly of amide-based macrocycles around the axle to form rotaxanes in up to 60% yields. Employing solely phosphorus-based functional groups as the hydrogen bond accepting groups on the thread, a bis(phosphinamide) template and a phosphine oxide-phosphinamide template afforded the corresponding rotaxanes in 18 and 15% yields, respectively. X-ray crystallography of the rotaxanes shows the presence of up to four intercomponent hydrogen bonds between the amide groups of the macrocycle and various hydrogen bond accepting groups on the thread, including rare examples of amide-to-phosphinamide, -thiophosphinamide, and -selenophosphinamide groups. With a phosphine oxide-phosphinamide thread, the solid-state structure of the rotaxane is remarkable, featuring no direct intercomponent hydrogen bonds but rather a hydrogen bond network involving water molecules that bridge the H-bonding groups of the macrocycle and thread through bifurcated hydrogen bonds. The incorporation of phosphorus-based functional groups into rotaxanes may prove useful for the development of molecular shuttles in which the macrocycle can be used to hinder or expose binding ligating sites for metal-based catalysts.     

Asymmetric benzoin condensation catalyzed by chiral rotaxanes tethering a thiazolium salt moiety via the cooperation of the component: can rotaxane be an effective reaction field?

Although some reactions on rotaxanes have been reported, the characteristic features of the rotaxanes providing unique reaction fields have hardly been studied, especially as catalyst. In our continuous studies on interlocked molecules such as rotaxanes and catenanes, we have noticed the importance of such interlocked structures with high freedom in functionalized materials such as molecular catalyst. For catalytic asymmetric benzoin condensations, two optically active rotaxanes possessing thiazolium salt moieties were prepared using the binaphthyl group as the chiral auxiliary. The benzoin condensations of aromatic aldehydes catalyzed by the chiral rotaxanes as catalysts gave optically active benzoins with ca. 30% ee in moderate to high chemical yields depending upon the structure of rotaxane and the reaction conditions employed. From the results, two intrarotaxane chirality transfers are confirmed: (i) through-space chirality transfer from wheel to axle and (ii) through-bond chirality transfer controlled with an achiral wheel. Because these asymmetric reaction fields are specific to the rotaxane structure, the importance and possibility of the "rotaxane field" as a particular reaction field is demonstrated in this work.     

A Dual‐Response [2]Rotaxane Based on a 1,2,3‐Triazole Ring as a Novel Recognition Station

Two novel multilevel switchable [2]rotaxanes containing an ammonium and a triazole station have been constructed by a Cu^I‐catalyzed azide–alkyne cycloaddition reaction. The macrocycle of [2]rotaxane containing a C6‐chain bridge between the two hydrogen bonding stations exhibits high selectivity for the ammonium cation in the protonated form. Interestingly, the macrocycle is able to interact with the two recognition stations when the bridge between them is shortened. Upon deprotonation of both [2]rotaxanes, the macrocycle moves towards the triazole recognition site due to the hydrogen‐bond interaction between the triazole nitrogen atoms and the amide groups in the macrocycle. Upon addition of chloride anion, the conformation of [2]rotaxane is changed because of the cooperative recognition of the chloride anion by a favorable hydrogen‐bond donor from both the macrocycle isophthalamide and thread triazole CH proton.     

Induction of Single‐Handed Helicity of Polyacetylenes Using Mechanically Chiral Rotaxanes as Chiral Sources

Effective induction of preferred‐handed helicity of polyacetylenes by pendant mechanically chiral rotaxanes is discussed. Polyacetylenes possessing optically active mechanically chiral rotaxanes in the side chains were synthesized by the polymerization of the corresponding enantiopure [2]rotaxane‐type ethynyl monomers prepared by the chiral‐phase HPLC separations. The CD Cotton effects revealed that the polyacetylenes took preferred‐handed helical conformations depending on the rotaxane chirality. The preferred‐handed helix was not disturbed by an additional chiral substituent on the rotaxane side chain. These results demonstrate the significance and utility of mechanically chiral rotaxanes for the effective construction of asymmetric fields.     

Electron-induced switching of the supramolecular chirality of optically active polythiophene aggregates

A chiral regioregular polythiophene (PT), poly[3-[4-((R)-4-ethyl-2-oxazolin-2-yl)phenyl]thiophene] (poly-1), forms chiral aggregates which exhibit a unique induced circular dichroism (ICD) in the pi-pi transition region derived from the supramolecular chirality in the presence of various poor solvents or metal salts in chloroform. We report here that the chirality of such supramolecular aggregates can be switched ("on" and "off") through electron transfer. We have found that upon the addition of copper(II) trifluoromethanesulfonate [Cu(OTf)(2)] to the chiral aggregates of poly-1 in a chloroform-acetonitrile mixture, the ICD disappears because of the oxidative doping of the poly-1 main chain, while a further addition of amines such as triethylenetetramine (TETA) induces undoping of the poly-1 which results in the reappearance of the ICDs. Therefore, the supramolecular chirality of the poly-1 assemblies was reversibly controlled by the addition or removal of an electron from the poly-1 main chain. This may be the first example of a reversible supramolecular chirality switch on chiral PT aggregates. We investigated the mechanism of the chirality switch through the doping and undoping process on the polymer main chain by means of absorption and CD spectroscopies, ESR, cyclic voltammetry, X-ray diffraction, and AFM measurements.     

Enantioselective Formation of 2‐Azetidinones by Ring‐Assisted Cyclization of Interlocked N‐(α‐Methyl)benzyl Fumaramides

The synthesis of optically active interlocked and non‐interlocked 2‐azetidinones by intramolecular cyclization of N‐(α‐methyl)benzyl fumaramide [2]rotaxanes is described. Two different strategies of asymmetric induction were tested in which the chiral group was located either proximal or distal to the reacting center of the thread. During these experiments, an interesting equilibration process inside the macrocyclic void occurred, thus leading to the cyclization through the (α‐methyl)benzyl carbon atom and giving rise to β‐lactams, with a quaternary carbon atom, in an enantio‐ and diastereocontrolled manner. This cyclization also proceeds in kinetically stable chiral pseudo[2]rotaxanes, thus allowing further dethreading to provide enantioenriched 3,4‐disubstituted trans‐2‐azetidinones. The stereochemical outcomes of the cyclizations inside and outside the macrocycle demonstrated noticeable differences.     

Dimers of cyclic carbonates: chirality recognition in battery solvents and energy storage

Dimers of ethylene carbonate and propylene carbonate are created in supersonic jet expansions and characterized by FTIR spectroscopy. Fermi resonances are switched on and off by dimerization. There is a unique centrosymmetric dimer of ethylene carbonate in a pronounced case of complementary chirality synchronization, contributing to its energy storage capacity at melting. Two chiral propylene carbonate molecules combine in more intricate ways. If they have the same handedness, one of them is forced into an axial conformation and the binding partner stays in the more stable equatorial structure. If they have opposite handedness, centrosymmetric dimers of either axial or equatorial conformations are formed. This suggests the usefulness of chirality control in elucidating ionic transport mechanisms in battery solvents and asymmetric catalysis in such solvents.     

Biogenetic Chiral Deep Eutectic Solvents that Produce Self-Assembled Chiroptical Materials

Deep eutectic solvents (DESs) show particular properties compared to ionic liquids and other traditional organic solvents. Controlled synthesis of chiral materials in DESs is unprecedented due to the complex interplays between DESs and solutes. In this work, all bio-derived chiral DESs were prepared using choline chloride or cyclodextrin as hydrogen bonding acceptors and natural chiral acids as donors, which performed as chiral matrices for the rational synthesis of chiroptical materials by taking advantage of the efficient chirality transfer between the DESs and solutes. In a very selective manner, building units with molecular pockets could facilitate strong binding affinity towards chiral acid components of DESs disregarding the presence of competitive hydrogen bonding acceptors. Chirality transfer from DESs to nanoassemblies leads to chirality amplification in the presence of minimal amounts of entrapped chiral acids, thanks to the spontaneous symmetry breaking of solutes during aggregation. This work utilizes chiral DESs to control supramolecular chirality, and illustrates the structural basis for the fabrication of DES-based chiral materials.     

Diverse Role of Solvents in Controlling Supramolecular Chirality

Supramolecular self-assembly stands for the spontaneous aggregation of small organic compounds or polymers into ordered structures at any scale. When being induced by inherent molecular chiral centers or ambient asymmetric factors, asymmetric spatial arrangement between building units shall occur, which is defined as supramolecular chirality. Except for molecular design, utilizing external stimulus factors to tune supramolecular chirality is a promising approach. In this Concept article, we particularly discuss the important role of solvents in manipulating the chirality of self-assembled systems. The impact of solvents on the chirality is generally based on three properties of solvents, i.e., chirality, polarity, and active coassembly with building blocks. Molecular self-assembly in chiral solvents could undergo the chirality transfer, exhibiting a chiral induction effect. Solvent polarity often determines intermolecular orientation. As a consequence, those building blocks with both polar and apolar segments might change their chirality depending on the solvent polarity. We elaborate the active participation of solvent molecules into ordered structures together with building blocks, where solvents and building blocks exhibit a coassembly manner. By specific treatments such as heating and cooling, solvents could be released or re-entrapped, allowing a smart control over supramolecular chirality. The solvent effect in manipulating two-dimensional chiral self-assemblies is then discussed. The perspective and future development in this research field are presented at last.     

Heterobifunctional Rotaxanes for Asymmetric Catalysis

Heterobifunctional rotaxanes serve as efficient catalysts for the addition of malonates to Michael acceptors. We report a series of four different heterobifunctional rotaxanes, featuring an amine‐based thread and a chiral 1,1′‐binaphthyl‐phosphoric‐acid‐based macrocycle. High‐level DFT calculations provided mechanistic insights and enabled rational catalyst improvements, leading to interlocked catalysts that surpass their non‐interlocked counterparts in terms of reaction rates and stereoselectivities.     

A molecular dynamics study of chirality transfer: The impact of a chiral solute on an achiral solvent

A solvation shell may adapt to the presence of a chiral solute by becoming chiral. The extent of this chirality transfer and its dependence on the solute and solvent characteristics are explored in this article. Molecular dynamics simulations of solvated chiral analytes form the basis of the analysis. The chirality induced in the solvent is assessed based on a series of related chirality indexes originally proposed by Osipov [M. A. Osipov et al., Mol. Phys. 84, 1193 (1995)]. Two solvents are considered: Ethanol and benzyl alcohol. Ethanol provides insight into chirality transfer when the solvent interacts with the solute primarily by a hydrogen bond. Several ethanol models have been considered starting with a nonpolarizable model, progressing to a fluctuating charge model, and finally, to a fully polarizable model. This progression provides some insights into the importance of solvent polarizability in the transfer of chirality. Benzyl alcohol, by virtue of the aromatic ring, increases the number of potential solvent-solute interactions. Thus, with these two solvents, the issue of compatibility between the solvent and solute is also considered. The solvation of three chiral solutes is examined: Styrene oxide, acenaphthenol, and n-(1-(4-bromophenyl)ethyl)pivalamide (PAMD). All three solutes have the possibility of hydrogen bonding with the solvent, the last two may also form ring-ring interactions, and the last also has multiple hydrogen bonding sites. For PAMD, the impact of conformational averaging is examined by comparing the chirality transfer about rigid and flexible solutes.     

Squaraine-derived rotaxanes: sterically protected fluorescent near-IR dyes

A squaraine dye with bulky end groups is employed as the thread component in two Leigh-type amide rotaxanes. The rotaxanes are synthesized in a simple two-step process. X-ray crystal structures of the rotaxanes show that the pyridyl-containing macrocycle is more rigid and wraps more tightly around the cyclobutene core of the squaraine thread compared to the isophthalamide-containing macrocycle. The rotaxanes exhibit photophysical properties that are similar to the precursor squaraine. The encapsulating macrocycle greatly increases the chemical stability of the squaraine thread and inhibits aggregation-induced broadening of its absorption spectrum. It should be possible to prepare squaraine-derived rotaxanes with improved properties for a wide range of photophysical, photochemical, and biomedical applications.     

Preparation and unique circular dichroism phenomena of urea-functionalized self-folding resorcinarenes bearing chiral termini through asymmetric hydrogen-bonding belts

Chiral macrocycles with eight (R)- and (S)-methylbenzylurea residues on the resorcinarene skeleton linked through a hexyl or dodecyl spacer having amide linkages have been prepared by the reactions of the corresponding octaamine derivative with (R)- and (S)-alpha-methylbenzylisocyanate, respectively. In chloroform, the urea-functionalized resorcinarenes with hexyl spacers form intramolecular hydrogen bonds by bundling the urea and amide residues in a cyclic fashion to give a self-folding cavitand. The urea and amide residues are cooperatively oriented in the same direction to result in asymmetric hydrogen-bonding belts. Unique circular dichroism (CD) bands are induced in the absorption wavelength ranges of the macrocyclic skeleton, caused by a chirality transmission from their chiral urea termini through hexyl spacers in the self-folded conformation. On the other hand, urea-functionalized resorcinarenes with a longer dodecyl spacer do not show such unique CD bands on the macrocycle, because of their weaker propensity for hydrogen bond formation. The characteristic CD bands of the urea-functionalized self-folding macrocycles disappeared upon complexation with anions such as chloride and bromide, reflecting breaking of the intramolecular hydrogen-bonding belts.     

Dynamic chirality, chirality transfer and aggregation behaviour of dithienylethene switches

The synthesis and characterisation of a series of chiral and achiral low molecular weight organogelators (LMWGs) based on bis-amide substituted dithienylethene photochromic switches is reported. The LMWGs gelate a range of solvents depending on the specific functionalisation of the hydrogen bonding amide groups. In mixtures of chiral and achiral LMWGs the stereochemical outcome of the chiral aggregation is determined by the chiral LMWG molecules in most cases. However, for the first time we demonstrate that the stereochemical outcome of the aggregation can be influenced by the achiral LWMG molecules in some cases. Furthermore specific π-π (and/or van der Waals) interactions of chiral LMWGs 1-3o with the solvent allow the solvent to influence the control of chirality of aggregation. This influence of the solvent has a dramatic effect on whether four- or two-gel states are available.     

‘Double chiral’ new members of calixsalen family

Synthesis and X-ray diffraction studies on the first examples of ‘double chiral’ calixsalens are presented. In these molecules, one can clearly distinguish two chiral zones. The first one is made by the macrocycle base, whereas the second chiral zone is set up of the additional chirality elements in the tail of the molecule. The ‘double chiral’ calixsalens are formed through cyclocondensation between chiral vicinal diamine of trans-1,2-diaminocyclohexane type and chiral C-5 substituted 2-hydroxyisophthalaldehyde derivatives. The absolute configuration of the dialdehyde did not affect the yield of the macrocyclization reaction. The presence of secondary amides in the tail part of the macrocycle leads to formation of hydrogen bonding network in the solid state, while sterical hindrance preserve interdigitation, thus, ‘double chiral’ calixsalens do not form aggregates typical for other calixsalens.     

Stiff, and sticky in the right places: the dramatic influence of preorganizing guest binding sites on the hydrogen bond-directed assembly of rotaxanes.

Structural rigidity and the preorganization of thread binding sites are shown to have a major influence on template efficiency in the synthesis of hydrogen bond-assembled rotaxanes. Preorganization is so effective, in fact, that with good hydrogen bond acceptors (amides) a "world record" yield of 97% for a [2]rotaxane is obtained. The truly remarkable feature of this efficient template, however, is that it allows even poor hydrogen bond acceptors (esters) to be used to prepare hydrogen bond-assembled rotaxanes, despite the presence of competing hydrogen bonding groups (anions) which bind the key intermediates at least 10000x more strongly than single, unorganized, ester groups! The structures of the rotaxanes are established unambiguously in solution by (1)H NMR spectroscopy and in the solid state by X-ray crystallography. As a series they provide unique experimental information regarding the nature of amide-ester hydrogen bonding interactions; in particular they suggest that in CDCl(3), amide-ester NH...O=C hydrogen bonds are approximately 1 kcal mol(-)(1) weaker than the corresponding amide-amide interactions.     

Infrared study of intercomponent interactions in a switchable hydrogen-bonded rotaxane

The macrocycle in rotaxane 1 is preferentially hydrogen bonded to the succinamide station in the neutral form, but can be moved to the naphthalimide station by one-electron reduction of the latter. The hydrogen bonding between the amide NH groups of the macrocycle and the C double bond O groups in the binding stations in the thread was studied with IR spectroscopy in different solvents in both states. In addition, the solvent effect on the vibrational frequencies was analyzed; a correlation with the solvent acceptor number (AN) was observed. The conformational switching upon reduction could be detected by monitoring the hydrogen-bond-induced shifts of the nu(CO) frequencies of the C double bond O groups of the succinamide and the reduced naphthalimide stations. The macrocycle was found to shield the encapsulated station from the solvent: wavenumbers of nu(CO) bands of the C double bond O groups residing inside the macrocycle cavity remain unaffected by the solvent polarity.     

Controlled Dynamic Helicity of a Folded Macrocycle Based on a Bisterephthalamide with a Twofold Z‐Shaped Structure

Dynamic helicity in a folded macrocycle and control of the helical preference are described. We designed macrocycle 1 with a dual mode of folding through the integration of two flexible units that are arranged twice to form a cyclic structure. As a folding unit, we used a terephthalamide skeleton and a Z‐shaped hydrocarbon: the former acted as a control unit to induce a preference of a particular sense of dynamic helicity and the latter was just a spacer. A terephthalamide unit provided a binding site for capturing a ditopic hydrogen‐bonding guest when it adopted helically folded syn forms (M/P). Thus, only the terephthalamide unit controlled the helical sense of dynamic helicity in a folded macrocycle through the supramolecular transmission of chirality upon complexation with a chiral ditopic guest. In addition, chirality on a host could also contribute to the control of the helical preference in a folded macrocycle, which led to exceptionally enhanced chiroptical signals.     

The effect of mechanical interlocking on crystal packing: predictions and testing

The first statistical analyses of the X-ray crystal structures of mechanically interlocked molecular architectures, the first molecular mechanics-based solid-state calculations on such structures and atomic force microscopy (AFM) experiments are used in combination to predict and test which types of benzylic amide macrocycle-containing rotaxanes possess mobile components in the crystalline phase and thus could form the basis of solid-state devices that function through mechanical motion at the molecular level. The statistical studies and calculations show that crystals formed by rotaxanes possess similarities and unanticipated differences with respect to the crystal packing of noninterlocked molecules. Trends in the rotaxane series correlate quantities related to crystal packing, molecular size, stoichiometry, and H-bonding. In accordance with the findings of Gavezzotti et al. for conventional molecular architectures, a principal component analysis (PCA) showed that three vectors related to the size, packing parameters, and stoichiometry are sufficient to describe the crystal properties of benzylic amide macrocycle-containing rotaxanes. When hydrogen bond-related quantities are included in a second PCA, they combine with the size and the stoichiometry vectors but not with packing-related parameters, indicating that the intramolecular "saturation" of the H-bonds (between the interlocked components) takes precedence over crystal assembly (i.e., intermolecular packing) in these systems. However, cluster analyses also suggest a major role for the energy of interaction between the macrocycle and its crystal environment. The identification of such a "privileged" interaction is of fundamental importance to the development of rotaxanes with in-crystal mobility of one or more of their interlocked components, a prerequisite for the exploitation of molecular level mechanical motion in the solid state. The set of trends found, together with the calculated energies, was used to propose guidelines for which benzylic amide macrocycle-containing rotaxanes are best suited to become building blocks for systems with mobile submolecular units in the crystalline phase. An experimental test of the predictive power of such guidelines was carried out using AFM on a rotaxane and its thread, identified by the study as a promising candidate for solid-state mobility. Intuitively, the rotaxane should be less mobile in the solid state since it has multiple sets of both hydrogen bond donors and acceptors that can form strong inter- and intramolecular H-bonds. Conversely, the thread has no hydrogen bond donors and cannot form such bonds. The AFM experiments, however, confirm the statistical analysis prediction that the rotaxane is considerably more mobile in the solid than the thread.