Probing rotaxane dynamics with 19F NMR/MRI: Unveiling the roles of mechanical bond and steric hindrance.

BACKGROUND: Deciphering the molecular dynamics (MD) of rotaxanes is crucial for designing and refining their applications in molecular devices. This study employed fluorine-19 nuclear magnetic resonance (19F NMR) and magnetic resonance imaging (MRI) to unveil the interplay between mechanical bonds and steric hindrance in a series of fluorinated rotaxanes. RESULTS: 1H/19F NMR revealed stable "Z"-shaped wheel conformations minimizing steric clashes and favoring π-π interactions with the axle. Utilizing fluorines and axle protons as reporters, 1H/19F relaxation rates and solid-state 19F NMR studies demonstrated that mechanical bond primarily governs wheel motion, while steric hindrance dictates axle movement. Intriguingly, mechanical bond mainly affects local axle groups, leaving distant ones minimally impacted. MD simulations corroborated these findings. Temperature-dependent 19F NMR indicated that energy input enhances rotational motion and wheel conformational transitions. Furthermore, the drastic increase in 19F relaxation rates upon mechanical bond formation and steric hindrance enables sensitive and selective 19F MRI visualization of MD changes. SIGNIFICANCE: This study, by elucidating the roles of internal and external factors on rotaxane molecular dynamics using 19F NMR/MRI, offers valuable insights that can advance the field of rotaxane-based molecular devices.

Dynamically Cross-linked Oligo[2]rotaxane Networks Mediated by Metal-Coordination.

Polyrotaxanes (PRs) have attracted significant research attention due to their unique topological structures and high degrees of conformational freedom. Herein, we take advantage of an oligo[2]rotaxane to  construct a novel class of dynamically cross-linked rotaxane network (DCRN) mediated by metal-coordination. The oligo[2]rotaxane skeleton offers several distinct advantages: In addition to retaining the merits of traditional polymer backbones, the ordered intramolecular motion of the [2]rotaxane motifs introduced dangling chains into the network, thereby enhancing the stretchability of the DCRN. Additionally, the dissociation of host‒guest recognition and subsequent sliding motion, along with the breakage of metal-coordination interactions, represented an integrated energy dissipation pathway to enhance mechanical properties. Moreover, the resulting DCRN demonstrated responsiveness to multiple stimuli and displayed exceptional self-healing capabilities in a gel state. Upon exposure to PPh3, which induced network deconstruction by breaking the coordinated cross-linking points, the oligo[2]rotaxane could be recovered, showcasing good recyclability. These findings demonstrate the untapped potential of the oligo[2]rotaxane as a polymer skeleton to develop DCRN and open the door to extend their advanced applications in intelligent mechanically interlocked materials.

Designed Synthesis of an Aluminum Molecular Ring Based Rotaxane and Polyrotaxane.

Mechanically interlocked molecules, such as rotaxanes, have drawn significant attention within supramolecular chemistry. Although a variety of macrocycles have been thoroughly explored in rotaxane synthesis, metal-organic macrocycles remain relatively under-investigated. Aluminum molecular rings, with their inner cavities and numerous binding sites, present a promising option for constructing rotaxanes. Here, we introduce an innovative "ring-donor···axle-acceptor" motif utilizing Al8 molecular rings, enabling the stepwise assembly of molecules, complexes, and polymers through tailored coordination chemistry. This novel approach can not only be applied to macrocycle-based systems like catenanes but also enhance specific functionalities progressively.

[5]Molecular Necklaces Formed Through Zn2+-Templated Binding of Macrocycles to Dynamically Formed Imines as Guest Recognition Sites.

Herein we demonstrate an "in-ring establishing" strategy for assembling interlocked molecules through dynamic imine formation, "establishing" the host recognition sites in situ. Using Zn2+ ions to template the assembly of a pyridine-containing macrocycle with semidumbbell-shaped triazole-containing aldehyde and amine derivatives, we obtained the corresponding [2]rotaxane in high yield (85%) after subsequent imine reduction (NaBH4) and amine protonation (NH4PF6). We performed the same three steps (assembly, reduction, protonation) to prepare a stable and highly symmetrical [5]molecular necklace ([5]MN) from 12 components (two almost-90°-oriented dialdehydes, two almost-90°-oriented diamines, four macrocycles, four Zn2+ ions) in an overall yield of 69%.

Mechanical Bond Induced Enhancement and Purification of Pyrene Emission in the Solid State.

To address key concerns on solid-state pyrene-based luminescent materials, we propose a novel and efficient mechanical bond strategy. This strategy results in a transformation from ACQ to AIE effect and a remarkable enhancement of pyrene emission in the solid state. Moreover, an unusual purification of emission is also achieved. Through computational calculation and experimental characterisation, finally determined by X-ray diffraction analysis, we prove that the excellent emissions result from mechanical bond induced refinement of molecular arrangements, including reduced π-π stacking, well-ordered packing and enhanced structural stability. This work demonstrates the potential of mechanical bond in the field of organic luminescent molecules, providing a new avenue for developing high-performance organic luminescent materials.

Studying Cation Exchange in {Cr7Co} Pseudorotaxanes: Preparatory Studies for Making Hybrid Molecular Machines.

In the design of dynamic supramolecular systems used in molecular machines, it is important to understand the binding preferences between the macrocycle and stations along the thread. Here, we apply 1H NMR spectroscopy to investigate the relative stabilities of a series of linear alkylammonium templated pseudorotaxanes with the general formula [H2NRR'][Cr7CoF8(O2CCH2 tBu)16] by exchanging the cation in solution. Our results show that the pseudorotaxanes are able to exchange threads via a dissociative mechanism. The position of equilibrium is dependent upon the ammonium cation and solvent used. Short chain primary ammonium cations are shown to be far less favourable macrocycle stations than secondary ammonium cations. Collision-induced dissociation mass spectrometry (CID-MS) has been used to look at disassembly of the pseudorotaxanes in a solvent-free environment and stability trends compared to those in acetone-d6. The energy needed to induce 50 % of the precursor ion loss (E50) is used and shows a similar trend to the equilibria measured by NMR. The relative stabilities of these hybrid inorganic-organic pseudo-rotaxanes are different to those of host-guest compounds involving crown ethers and this may be valuable for the design of molecular machines.

Ether Naphthotube Host-Guest Complexes and [2]Rotaxanes with Dications.

The interactions between ether naphthotube and a series of dication guests in organic solution were investigated. It was found that ether naphthotube formed stable host-guest complexes selectively with these guests in a 1 : 1 stoichiometric ratio with association constants ranging from 102 to 106 M-1, which were confirmed by 1H-NMR spectra and ITC experiments. The host-guest interactions are driven by enthalpy change as the entropic factors are unfavorable. Positive correlations between ΔH and ΔS have been observed in the host-guest complexes. Furthermore, the para-substitution of the guests can significantly affect the binding affinities through a combination of field/inductive and resonance effects by following a linear free energy relationship. Based on the host-guest complexes composed of ether naphthotube and organic cations, two interlocked [2]rotaxanes were prepared by cationization reaction and Huisgen cycloaddition between the cations and the stopper components. The ether naphthotube-based host-guest complexes are useful for creating sophisticated interlocked molecules.

Polymerizable rotaxane of cucurbituril protecting dopamine based adhesive hydrogels.

The catechol moiety found within mussel proteins plays a pivotal role in enhancing their adhesive properties. Nonetheless, catechol compounds, such as dopamine (DOP) derivatives, are susceptible to oxidation, leading to the formation of quinone. This oxidation process poses a significant challenge in the development of DOP-based hydrogels, hampering their adhesion capabilities and hindering polymerization. To protect DOP moieties from oxidation, DOP and N-(3-aminopropyl)methacrylamide (AMA) moieties were grafted onto the side groups of biocompatible poly(glutamic acid) (PGA). Subsequently, the DOP unit, serving as a second guest, would be captured by a polymerizable rotaxane of cucurbituril (CB[n]), in which the host molecule CB[8] complexed with the first guest, polymerizable methyl viologen (MV), forming a protective function and dynamic cross-linking. Upon exposure to light curing, a composite network emerged through the synergy of covalent cross-linking and supramolecular host-guest complexation of DOP with CB[8]. The generated complexation between DOP and CB[8] could protect the DOP moieties, resulting in photocured hydrogels with exceptional adhesive strength and remarkable tensile capabilities. Moreover, 3D printing technology was used to create various models with these DOP-based hydrogels, demonstrating their promising applications in future.

Crown-ether threaded covalent organic polyrotaxane framework (COPF) towards synergistic crown/Zn2+/photothermal/photodynamic antibacterial and infected wound healing therapy.

Controllable preparation of materials with new structure has always been the top priority of polymer materials science research. Here, the supramolecular binding strategy is adopted to develop covalent organic frameworks (COFs) with novel structures and functions. Based on this, a two-dimensional crown-ether ring threaded covalent organic framework (COF), denoted as Crown-COPF with intrinsic photothermal (PTT) and photodynamic (PDT) therapeutic capacity, was facilely developed using crown-ether threaded rotaxane and porphyrin as building blocks. Crown-COPF with discrete mechanically interlocked blocks in the open pore could be used as a molecular machine, in which crown-ether served as the wheel sliding along the axle under the laser stimulation. As a result, Crown-COPF combining with the bactericidal power of crown ether displayed a significant photothermal and photodynamic antibacterial activity towards both the Gram-negative (Escherichia coli) and Gram-positive (Staphylococcus aureus), far exceeding the traditional Crown-free COF. Noteworthily, the bactericidal performance could be further enhanced via impregnation of Zn2+ ions (Crown-COPF-Zn) flexible coordinated with the multiple coordination sites (crown-ether, bipyridine, and porphyrin), which not only endow the positive charge with the skeleton, enhancing its ability to bind to the bacterial membrane, but also introduce the bactericidal ability of zinc ions. Notably, in vivo experiments on mice with back infections indicates Crown-COPF-Zn with self-adaptive multinuclear zinc center, could effectively promote the repairing of wounds. This study paves a new avenue for the effectively preparation of porous polymers with brand new structure, which provides opportunities for COF and mechanically interlocked polymers (MIPs) research and applications.

Solution and Solvent-Free Stopper Exchange Reactions for the Preparation of Pillar[5]arene-containing [2] and [3]Rotaxanes.

Diamine reagents have been used to functionalize a [2]rotaxane building block bearing an activated pentafluorophenyl ester stopper. Upon a first acylation, an intermediate host-guest complex with a terminal amine function is obtained. Dissociation of the intermediate occurs in solution and acylation of the released axle generates a [2]rotaxane with an elongated axle subunit. In contrast, the corresponding [3]rotaxane can be obtained if the reaction conditions are appropriate to stabilize the inclusion complex of the mono-amine intermediate and the pillar[5]arene. This is the case when the stopper exchange is performed under mechanochemical solvent-free conditions. Alternatively, if the newly introduced terminal amide group is large enough to prevent the dissociation, the second acylation provides exclusively a [3]rotaxane. On the other hand, detailed conformational analysis has been also carried out by variable temperature NMR investigations. A complete understanding of the shuttling motions of the pillar[5]arene subunit along the axles of the rotaxanes reported therein has been achieved with the help of density functional theory calculations.

Exploiting the Mechanical Bond Effect for Enhanced Molecular Recognition and Sensing.

The ubiquity of charged species in biological and industrial processes has resulted in ever-increasing interest in their selective recognition, detection, and environmental remediation. Building on the established coordination chemistry principles of the chelate and macrocyclic effects, and host preorganization, supramolecular chemists seek to construct specific 3D binding cavities reminiscent of biotic systems to enhance host-guest binding affinity and selectivity. Mechanically interlocked molecules (MIMs) present a wholly unique platform for synthetic host design, wherein topologies afforded by the mechanical bond enable the decoration of 3D cavities for non-covalent interactions with a range of target guest geometries. Notably, MIM host systems exhibit mechanical bond effect augmented affinities and selectivities for a variety of charged guest species, compared to non-interlocked acyclic and macrocycle host analogs. Furthermore, the modular nature of MIM synthesis facilitates incorporation of optical and electrochemical reporter groups, enabling fabrication of highly sensitive and specific molecular sensors. This review discusses the development of recognition and sensing MIMs, from the first reports in the late 20th century through to the present day, delineating how their topologically preorganized and dynamic host cavities enhance charged guest recognition and sensing, demonstrating the mechanical bond effect as a potent tool in future chemosensing materials.

Threading a Linear Molecule Through a Macrocycle Thanks to Boron: Optical Properties of the Threaded Species and Synthesis of a Rotaxane.

Two BODIPYs and two boron ß-diketonates were threaded through a macrocycle bearing a 2,2'-biphenol unit, showing thus the ability of boron to act as a gathering atom. The new threaded species were characterized by 1D and 2D NMR spectroscopy as well as by X-ray crystallography for one of them and their properties rationalized with quantum chemistry to unravel the vibronic contributions. The BODIPYs exhibited interesting fluorescence features with quantum yields up to 91 % and enhanced photostability compared to their non-threaded homologues. A rotaxane was synthesized using this threading strategy after stoppering and removing the boron with potassium hydroxide.

Tunable Nano-Bending Structures of Loosened/Tightened Lassos with Bi-Stable Vibration-Induced Emissions for Multi-Manipulations of White-Light Emissions and Sensor Applications.

The first tunable nano-bending structures of [1]rotaxane containing a single-fluorophoric N,N'-diphenyl-dihydrodibenzo[a,c]phenazine (DPAC) moiety (i.e., [1]RA) are developed as a loosened lasso structure to feature the bright white-light emission [CIE (0.27, 0.33), Φ = 21.2%] in THF solution, where bi-stable states of bending and twisted structures of DPAC unit in [1]RA produce cyan and orange emissions at 480 and 600 nm, respectively. With acid/base controls, tunable loosened/tightened nano-loops of corresponding [1]rotaxanes (i.e., [1]RA/[1]RB) can be achieved via the shuttling of macrocycles reversibly, and thus to adjust their respective white-light/cyan emissions, where the cyan emission of [1]RB is obtained due to the largest conformational constraint of DPAC moiety in its bending form of [1]RB with a tightened lasso structure. Additionally, the non-interlocked analog M-Boc only shows the orange emission, revealing the twisted form of DPAC fluorophore in M-Boc without any conformational constraint. Moreover, the utilization of solvents (with different viscosities and polarities), temperatures, and water fractions could serve as effective tools to adjust the bi-stable vibration-induced emission (VIE) colors of [1]rotaxanes. Finally, tuning ratiometric emission colors of adaptive conformations of DPAC moieties by altering nano-bending structures in [1]rotaxanes and external stimuli can be further developed as intelligent temperature and viscosity sensor materials.

Dendrimers: Exploring Their Wide Structural Variety and Applications.

Dendrimers constitute a distinctive category of synthetic materials that bear resemblance to proteins in various aspects, such as discrete structural organization, globular morphology, and nanoscale dimensions. Remarkably, these attributes coexist with the capacity for facile large-scale production. Due to these advantages, the realm of dendrimers has undergone substantial advancement since their inception in the 1980s. Numerous reviews have been dedicated to elucidating this subject comprehensively, delving into the properties and applications of quintessential dendrimer varieties like PAMAM, PPI, and others. Nevertheless, the contemporary landscape of dendrimers transcends these early paradigms, witnessing the emergence of a diverse array of novel dendritic architectures in recent years. In this review, we aim to present a comprehensive panorama of the expansive domain of dendrimers. As such, our focus lies in discussing the key attributes and applications of the predominant types of dendrimers existing today. We will commence with the conventional variants and progressively delve into the more pioneering ones, including Janus, supramolecular, shape-persistent, and rotaxane dendrimers.

An Interlocked Figure-of-Eight Molecular Shuttle.

Here is reported the synthesis and characterization of an interlocked figure-of-eight rotaxane molecular shuttle from a dibenzo-24-crown-8 (DB24C8) derivative. This latter bears two molecular chains, whose extremities are able to react together by click chemistry. One of the two substituting chain holds an ammonium function aimed at driving the self-entanglement through the complexation of the DB24C8 moiety. In the targeted figure-of-eight rotaxane, shuttling of the DB24C8 along the threaded axle from the best ammonium station to the weaker binding site triazolium was performed through deprotonation or deprotonation-then-carbamoylation of the ammonium. This way, two discrete co-conformational states were obtained, in which the folding and size of the two loops could be changed.

Tunable Fluorescence and Morphology of Aggregates Built from a Mechanically Bonded Amphiphilic Bistable [2]Rotaxane.

Advanced Organic Chemical Materials Co-constructed Mechanically bonded amphiphiles (MBAs), also known as mechanically interlocked molecules (MIMs), have emerged as an important kind of functional building block for the construction of artificial molecular machines and soft materials. Herein, a novel MBA, i. e., bistable [2]rotaxane H2 was designed and synthesized. In the solution state, H2 demonstrated pH and metal ion-responsive emissions due to the presence of a distance-dependent photoinduced electron transfer (PET) process and the fluorescence resonance energy transfer (FRET) process, respectively. Importantly, the amphiphilic feature of H2 has endowed it with unique self-assembly capability, and nanospheres were obtained in a mixed H2 O/CH3 CN solvent. Moreover, the morphology of H2 aggregates can be tuned from nanospheres to vesicles due to the pH-controlled shuttling motion-induced alternation of H2 amphiphilicity. Interestingly, larger spheres with novel pearl-chain-like structures from H2 were observed after adding stoichiometric Zn2+ . In particular, H2 shows pH-responsive emissions in its aggregation state, allowing the visualization of the shuttling movement by just naked eyes. It is assumed that the well-designed [2]rotaxane, and particularly the proposed concept of MBA shown here, will further enrich the families of MIMs, offering prospects for synthesizing more MIMs with novel assembly capabilities and bottom-up building dynamic smart materials with unprecedented functions.

Catenane and Rotaxane Synthesis from Cucurbit[6]uril-Mediated Azide-Alkyne Cycloaddition.

The chemistry of mechanically interlocked molecules (MIMs) such as catenane and rotaxane is full of new opportunities for the presence of a mechanical bond, and the efficient synthesis of these molecules is therefore of fundamental importance in realizing their unique properties and functions. While many different types of preorganizing interactions and covalent bond formation strategies have been exploited in MIMs synthesis, the use of cucurbit[6]uril (CB[6]) in simultaneously templating macrocycle interlocking and catalyzing the covalent formation of the interlocked components is particularly advantageous in accessing high-order catenanes and rotaxanes. In this review, catenane and rotaxane obtained from CB[6]-catalyzed azide-alkyne cycloaddition will be discussed, with special emphasis on the synthetic strategies employed for obtaining complex [n]rotaxanes and [n]catenanes, as well as their properties and functions.

Rotaxane Formation of Multicyclic Polydimethylsiloxane in a Silicone Network: A Step toward Constructing "Macro-Rotaxanes" from High-Molecular-Weight Axle and Wheel Components.

Rotaxanes consisting of a high-molecular-weight axle and wheel components (macro-rotaxanes) have high structural freedom, and are attractive for soft-material applications. However, their synthesis remains underexplored. Here, we investigated macro-rotaxane formation by the topological trapping of multicyclic polydimethylsiloxanes (mc-PDMSs) in silicone networks. mc-PDMS with different numbers of cyclic units and ring sizes was synthesized by cyclopolymerization of a α,ω-norbornenyl-functionalized PDMS. Silicone networks were prepared in the presence of 10-60 wt % mc-PDMS, and the trapping efficiency of mc-PDMS was determined. In contrast to monocyclic PDMS, mc-PDMSs with more cyclic units and larger ring sizes can be quantitatively trapped in the network as macro-rotaxanes. The damping performance of a 60 wt % mc-PDMS-blended silicone network was evaluated, revealing a higher tan δ value than the bare PDMS network. Thus, macro-rotaxanes are promising as non-leaching additives for network polymers.

EPR Sensing of a Cation Species by Aza-Crown Ethers Incorporating a Persistent Nitroxidic Radical Unit.

New nitroxides based on aza-crown ethers were prepared and employed as selective sensors for the detection of inorganic and organic cations by EPR analysis of the corresponding host-guest complexes. The nitroxide unit behaves as a sensitive probe for a number of alkali and alkaline earth metal cations affording EPR spectra differing in the value of nitrogen hyperfine constants and in the appearance of splitted signals due to the non-zero nuclear spin of some metal cation upon complexation. Owing to the remarkable EPR spectral differences between the host and the corresponding cation complex the new macrocycles are likely to act as multitasking tools to recognize several cationic species. EPR behaviour of the larger nitroxide azacrown 1⋅ when acting as a wheel in a radical synthetic bistable [2]rotaxane containing both secondary dialkylammonium and 1,2-bis(pyridinium) molecular stations, was also investigated. Reversible movements of the macrocycle between the two recognition sites in the rotaxane were promptly revealed by EPR, which shows significant changes either in nitrogen coupling constant values (aN ) or in the spectral shape in the two rotaxane co-conformations.

Platinum Metallacycle-Based Molecular Recognition: Establishment and Application in Spontaneous Formation of a [2]Rotaxane with Light-Harvesting Property.

Macrocyclic molecule-based host-guest systems, which provide contributions for the design and construction of functional supramolecular structures, have gained increasing attention in recent years. In particular, platinum(II) metallacycle-based host-guest systems provide opportunities for chemical scientists to prepare novel materials with various functions and structures due to the well-defined shapes and cavity sizes of platinum(II) metallacycles. However, the research on platinum(II) metallacycle-based host-guest systems has been given little attention. In this article, we demonstrate the host-guest complexation between a platinum(II) metallacycle and a polycyclic aromatic hydrocarbon molecule, naphthalene. Taking advantage of metallacycle-based host-guest interactions and the dynamic property of reversible Pt coordination bonds, a [2]rotaxane is efficiently prepared by employing a template-directed clipping procedure. The [2]rotaxane is further applied to the fabrication of an efficient light-harvesting system with multi-step energy transfer process. This work comprises an important supplement to macrocycle-based host-guest systems and demonstrates a strategy for efficient production of well-defined mechanically interlocked molecules with practical values.