Mechanical Bonding Research Articles

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

BackgroundDeciphering 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. Results1H/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. SignificanceThis 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.

Polycatenanes Formed of Self‐Assembled Metal‐Organic Cages

AbstractPoly‐[n]‐catenanes (PCs) self‐assembled of three‐dimensional (3D) metal organic cages (MOCs) (hereafter referred to as PCs‐MOCs) are a relatively new class of mechanically interlocked molecules (MIMs) that combine the properties of MOCs and polymers. The synthesis of PCs‐MOCs is challenging because of the difficulties associated with interlocking MOCs, the occurrence of multiple weak supramolecular electrostatic interactions between cages, and the importance of solvent templating effects. The high density of mechanical bonds interlocking the MOCs endows the MOCs with mechanical and physical properties such as enhanced stability, responsive dynamic behavior and low solubility, which can unlock new functional properties. In this Minireview, we highlight the benefit of interlocking MOCs in the formation of PCs‐MOCs structures as well as the synthetic approaches exploited in their preparation, from thermodynamic to kinetic methods, both in the solution and solid‐states. Examples of PCs‐MOCs self‐assembled from various types of nanosized cages (i.e., tetrahedral, trigonal prismatic, octahedral and icosahedral) are described in this article, providing an overview of the research carried out in this area. The focus is on the structure–property relationship with examples of functional applications such as electron conductivity, X‐ray attenuation, gas adsorption and molecular sensing. We believe that the structural and functional aspects of the reviewed PCs‐MOCs will attract chemists in this research field with great potential as new functional materials in nanotechnological disciplines such as gas adsorption, sensing and photophysical properties such as X‐ray attenuation or electron conductivity.

Polycatenanes Formed of Self-Assembled Metal-Organic Cages.

Poly-[n]-catenanes (PCs) self-assembled of three-dimensional (3D) metal organic cages (MOCs) (hereafter referred to as PCs-MOCs) are a relatively new class of mechanically interlocked molecules (MIMs) that combine the properties of MOCs and polymers. The synthesis of PCs-MOCs is challenging because of the difficulties associated with interlocking MOCs, the occurrence of multiple weak supramolecular electrostatic interactions between cages, and the importance of solvent templating effects. The high density of mechanical bonds interlocking the MOCs endows the MOCs with mechanical and physical properties such as enhanced stability, responsive dynamic behavior and low solubility, which can unlock new functional properties. In this Minireview, we highlight the benefit of interlocking MOCs in the formation of PCs-MOCs structures as well as the synthetic approaches exploited in their preparation, from thermodynamic to kinetic methods, both in the solution and solid-states. Examples of PCs-MOCs self-assembled from various types of nanosized cages (i.e., tetrahedral, trigonal prismatic, octahedral and icosahedral) are described in this article, providing an overview of the research carried out in this area. The focus is on the structure-property relationship with examples of functional applications such as electron conductivity, X-ray attenuation, gas adsorption and molecular sensing. We believe that the structural and functional aspects of the reviewed PCs-MOCs will attract chemists in this research field with great potential as new functional materials in nanotechnological disciplines such as gas adsorption, sensing and photophysical properties such as X-ray attenuation or electron conductivity.

Stimuli-responsive mechanically interlocked polymer wrinkles

Artificial wrinkles, especially those with responsive erasure/regeneration behaviors have gained extensive interest due to their potential in smart applications. However, current wrinkle modulation methods primarily rely on network rearrangement, causing bottlenecks in in situ wrinkle regeneration. Herein, we report a dually cross-linked network wherein [2]rotaxane cross-link can dissipate stress within the wrinkles through its sliding motion without disrupting the network, and quadruple H-bonding cross-link comparatively highlight the advantages of [2]rotaxane modulation. Acid stimulation dissociates quadruple H-bonding and destructs network, swiftly eliminating the wrinkles. However, the regeneration process necessitates network rearrangement, making in situ recovery unfeasible. By contrast, alkaline stimulation disrupts host–guest recognition, and subsequent intramolecular motion of [2]rotaxane dissipate energy to eliminate wrinkles gradually. The always intact network allows for the in situ recovery of surface microstructures. The responsive behaviors of quadruple H-bonding and mechanical bond are orthogonal, and their combination leads to wrinkles with multiple but accurate responsiveness.

Urea-Based [2]Rotaxanes as Effective Phase-Transfer Organocatalysts: Hydrogen-Bonding Cooperative Activation Enabled by the Mechanical Bond.

We finely designed a set of [2]rotaxanes with urea threads and tested them as hydrogen-bonding phase-transfer catalysts in two different nucleophilic substitutions requiring the activation of the reactant fluoride anion. The [2]rotaxane bearing a fluorinated macrocycle and a fluorine-containing urea thread displayed significantly enhanced catalytic activity in comparison with the combination of both noninterlocked components. This fact highlights the notably beneficial role of the mechanical bond, cooperatively activating the processes through hydrogen-bonding interactions.

Fabrication of TiN Coatings Deposited on Laser Shock Micro-Textured Substrates for Improving the Interface Adhesion Properties of Coatings.

This paper aims to investigate the strengthening mechanism of laser shock peening on the interfacial bonding properties between TiN coatings and TC4 titanium alloy substrates. The different surface textures were induced by LSP on a TC4 titanium alloy substrate. Subsequently, titanium nitride (TiN) coatings were deposited on the surface texture. A scratch test and reciprocating sliding wear assessment were conducted to evaluate the impact of LSP on the interfacial bonding properties and wear performance of the coatings. The experimental results demonstrated that the adhesion of TiN coatings deposited on the surface texture formed by laser shock peening was significantly enhanced. The efficacy of laser shock treatment in reducing wear rates was found to be significantly enhanced in cases of both increased spot overlapping rate and increased laser power density. The surface texture created using laser parameters of 6.43 GW/cm2 and a 50% overlapping rate was found to have the most significant effect on improving the adhesion and anti-wear properties of the coating. The laser shock texture was identified as the main contributor to this improvement, providing a large interfacial contact area and a mechanical bond between the coating and the substrate. This bond inhibited the initiation and propagation of micro-cracks caused by the concentration of internal stress and interfacial stress of the coating.

Cover Feature: Mechanical Bond Induced Enhancement and Purification of Pyrene Emission in the Solid State (Chem. Eur. J. 42/2024)

Cover Feature: Mechanical Bond Induced Enhancement and Purification of Pyrene Emission in the Solid State (Chem. Eur. J. 42/2024)

Synergistic effect of carbonation and dry–wet cycles on the adhesion, elastic modulus, and dimensional stability of rendering mortars – A multiscale approach

This study explored the combined effects of drying and wetting cycles with carbonation aging on rendering mortars and investigated mechanical properties, bond strength, dimensional stability, and durability at the macro and nanoscale levels. The rendered mortars were evaluated individually and applied to a ceramic substrate. The prepared samples were cured for 150 days, carbonated (5 % CO2 and an RH of 60 %), and underwent 20 drying–wetting cycles. Carbonation shrinks the mortar, which can be completely reversed after the first drying–wetting cycle. Exposing the mortar to drying–wetting cycles suppresses the improvements in the bond strength and modulus of elasticity attributed to carbonation. The nanoscale tests confirmed the results measured in the macroscale. In conclusion, this paper showed that changes in the render caused by carbonation may be reversed after wetting and drying cycles.

Mechanical Interatomic Bond Formation in Ethanol and Methanol-Ethanol Mixture by Laser-Driven Shock Waves.

Molecules, which were predicted to be produced by C-C or C-O bond formation between ethanol molecules induced by a laser-driven shock wave, were identified by gas chromatography-mass spectrometry. Moreover, the laser irradiation of a methanol-ethanol mixture revealed the formation of C-C and C-O bonds between both components. Particularly, four hemiacetals (methoxymethanol, 1-methoxyethanol, ethoxymethanol, and 1-ethoxyethanol) were identified in the Ar-saturated alcohol samples, whereas acetalization dominated sufficiently in the CO2-saturated samples, significantly reducing the hemiacetals. It was verified that some molecules were produced by the dropout of an ethanol part during the C-C or C-O bond formation, supporting the contribution of laser-driven shock waves.

Experimental and numerical study of underwater laser transmission welding

This work demonstrates the feasibility of the underwater laser transmission welding (LTW) of polycarbonate sheets. The experiments are performed to investigate the effect of water depth, laser power, beam diameter, and scan speed on the weld strength, weld dimensions, and bond morphology. The results of mechanical properties and bond morphology of the weld joint in underwater are compared with air environment. The lap shear tests are performed to obtain the shear force–displacement of the welded joints. A three-dimensional (3-D) numerical model is developed to estimate the interface temperature in the underwater condition, which is validated by comparing the numerical weld width and weld depth with their corresponding experimental value. The bond morphology of the weldments is analyzed by the optical microscope and scanning electron microscopy (SEM). The results show that a maximum mean breaking force of 567.5 N is obtained at the 20 mm water depth which is 6 % higher than air due to lower thermal degradation and wider bubble-less region inside the welded region.

A Stretchable and Tough Graphene Film Enabled by Mechanical Bond.

The pursuit of fabricating high-performance graphene films has aroused considerable attention due to their potential for practical applications. However, developing both stretchable and tough graphene films remains a formidable challenge. To address this issue, we herein introduce mechanical bond to comprehensively improve the mechanical properties of graphene films, utilizing [2]rotaxane as the bridging unit. Under external force, the [2]rotaxane cross-link undergoes intramolecular motion, releasing hidden chain and increasing the interlayer slip distance between graphene nanosheets. Compared with graphene films without [2]rotaxane cross-linking, the presence of mechanical bond not only boosted the strength of graphene films (247.3 vs 74.8 MPa) but also markedly promoted the tensile strain (23.6 vs 10.2 %) and toughness (23.9 vs 4.0 MJ/m3). Notably, the achieved tensile strain sets a record high and the toughness surpasses most reported results, rendering the graphene films suitable for applications as flexible electrodes. Even when the films were stretched within a 20 % strain and repeatedly bent vertically, the light-emitting diodes maintained an on-state with little changes in brightness. Additionally, the film electrodes effectively actuated mechanical joints, enabling uninterrupted grasping movements. Therefore, the study holds promise for expanding the application of graphene films and simultaneously inspiring the development of other high-performance two-dimensional films.

A Stretchable and Tough Graphene Film Enabled by Mechanical Bond

AbstractThe pursuit of fabricating high‐performance graphene films has aroused considerable attention due to their potential for practical applications. However, developing both stretchable and tough graphene films remains a formidable challenge. To address this issue, we herein introduce mechanical bond to comprehensively improve the mechanical properties of graphene films, utilizing [2]rotaxane as the bridging unit. Under external force, the [2]rotaxane cross‐link undergoes intramolecular motion, releasing hidden chain and increasing the interlayer slip distance between graphene nanosheets. Compared with graphene films without [2]rotaxane cross‐linking, the presence of mechanical bond not only boosted the strength of graphene films (247.3 vs 74.8 MPa) but also markedly promoted the tensile strain (23.6 vs 10.2 %) and toughness (23.9 vs 4.0 MJ/m3). Notably, the achieved tensile strain sets a record high and the toughness surpasses most reported results, rendering the graphene films suitable for applications as flexible electrodes. Even when the films were stretched within a 20 % strain and repeatedly bent vertically, the light‐emitting diodes maintained an on‐state with little changes in brightness. Additionally, the film electrodes effectively actuated mechanical joints, enabling uninterrupted grasping movements. Therefore, the study holds promise for expanding the application of graphene films and simultaneously inspiring the development of other high‐performance two‐dimensional films.

The End of the Beginning of Mechanical Stereochemistry.

ConspectusStereochemistry has played a key role in the development of synthetic chemistry for the simple reason that the function and properties of most molecules, from medicine to materials science, depend on their shape and thus the stereoisomer used. However, despite the potential for rotaxanes and catenanes to display unusual forms of stereochemistry being identified as early as 1961, this aspect of the mechanical bond remained underexplored and underexploited; until 2014 it was only possible to access chiral rotaxanes and catenanes whose stereoisomerism is solely attributable to the mechanical bond using chiral stationary phase high performance liquid chromatography, which limited their production on scale and thus inhibited the investigation of their properties and applications. Furthermore, the stereogenic units of such molecules and analogues were often poorly described, which made it hard to fully articulate both what had been achieved in the field and what problems were left to solve. Relatively recently, methods to access rotaxanes and catenanes that display mechanical stereochemistry selectively have been developed, making these intriguing structures available for study in a range of prototypical applications including catalysis, sensing, and as chiral luminophores.In this Account, we briefly discuss the history of mechanical stereochemistry, beginning in 1961 when the potential for mechanical stereoisomerism was first identified, before defining how mechanical stereochemistry arises from a structural point of view. Building on this, using simple stereochemical arguments, we confirm that the complete set of unique stereogenic units of two-component rotaxanes and catenanes have finally been identified and categorized unambiguously, with the last being identified only in 2024. After pausing to discuss some of the stereochemical curiosities that arise when molecules contain both covalent and mechanical stereogenic units, and the potential for stereoisomerism to arise due to co-conformational movement, we use our stereochemical framework to summarize our efforts to develop conceptually general approaches to [2]catenanes and [2]rotaxanes containing all of the possible mechanical stereogenic units. In particular, we highlight how the nature of a mechanical stereogenic unit affects the available strategies for their stereoselective synthesis. We finish by highlighting recent prototypical chemical applications of interlocked molecules that rely on their mechanical stereochemistry, before discussing future directions and challenges.Taken together, we propose that the transition of such molecules from being hard to make and poorly described, to being available in high stereopurity using clearly articulated methodological and stereochemical concepts suggests that the field is finally maturing. Thus, we are now coming to the end of the beginning of mechanical stereochemistry. The stage is now set for such molecules to play a functional role in a range of areas, indeed in any chemical or physical application where control over molecular shape is required.

Water and Air Stable Copper(I) Complexes of Tetracationic Catenane Ligands for Oxidative C-C Cross-Coupling.

Aqueous soluble and stable Cu(I) molecular catalysts featuring a catenane ligand composed of two dicationic, mutually repelling but mechanically interlocked macrocycles are reported. The ligand interlocking not only fine-tunes the coordination sphere and kinetically stabilizes the Cu(I) against air oxidation and disproportionation, but also buries the hydrophobic portions of the ligands and prevents their dissociation which are necessary for their good water solubility and a sustained activity. These catenane Cu(I) complexes can catalyze the oxidative C-C coupling of indoles and tetrahydroisoquinolines in water, using H2O2 as a green oxidant with a good substrate scope. The successful use of catenane ligands in exploiting aqueous Cu(I) catalysis thus highlights the many unexplored potential of mechanical bond as a design element for exploring transition metal catalysis under challenging conditions.

Water and Air Stable Copper(I) Complexes of Tetracationic Catenane Ligands for Oxidative C−C Cross‐Coupling

AbstractAqueous soluble and stable Cu(I) molecular catalysts featuring a catenane ligand composed of two dicationic, mutually repelling but mechanically interlocked macrocycles are reported. The ligand interlocking not only fine‐tunes the coordination sphere and kinetically stabilizes the Cu(I) against air oxidation and disproportionation, but also buries the hydrophobic portions of the ligands and prevents their dissociation which are necessary for their good water solubility and a sustained activity. These catenane Cu(I) complexes can catalyze the oxidative C−C coupling of indoles and tetrahydroisoquinolines in water, using H2O2 as a green oxidant with a good substrate scope. The successful use of catenane ligands in exploiting aqueous Cu(I) catalysis thus highlights the many unexplored potential of mechanical bond as a design element for exploring transition metal catalysis under challenging conditions.

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.

Conformational and Substitution Effects on the Donor and Reducing Strength of Tin(II) Porphyrinogens.

Meso-octaalkylcalix[4]pyrrolates are a class of redox-active porphyrinogen ligands. They have been well established in d- and f-block chemistry for over three decades but have only recently been introduced as ligands for p-block elements. Here, we present a study on the influence of meso-substituents on the redox chemistry of calix[4]pyrrolato stannate(II) dianions [2R]2- (R=Me, Et). Expansion of the normal-mode structural decomposition (NSD) method, well known for porphyrin chemistry, provides insights into the ligand conformation of a calix[4]pyrrolato p-block complex. Combined with the results of spectroscopic donor scaling, electrochemical studies, and quantum mechanical bond analysis tools, subtle but significant substitution and conformational effects on the electronic structure are revealed. Exploiting this knowledge rationalizes the role of this class of tin(II) dianions to act as potent reducing agents, but can also be expanded for other central elements. Photoexcitation boosts this reactivity further, allowing for the reduction of even challenging chlorobenzene.

In vitro Investigation of Resin Tag Lengths of Three Commercially Available Pit and Fissure Sealants.

The aim of this in vitro study was to perform a comparative evaluation of the length of resin tags produced by three different types of pit and fissure sealants (Embrace WetBond, Helioseal Clear, and Fuji VII) using scanning electron microscopy. Thirty extracted mandibular premolars were randomly divided into three groups of ten. Each group was treated with one of the sealants - Embrace WetBond, Helioseal Clear, or Fuji VII. Following cleaning and preparation, the sealants were applied according to the manufacturer's instructions. Teeth were then sectioned and prepared for SEM investigation, and the length of resin tags was measured. Scanning electron microscopy revealed Embrace WetBond produced significantly longer resin tags than Helioseal Clear and Fuji VII. The study concludes that Embrace WetBond sealant exhibited the longest resin tags, which may suggest a stronger mechanical bond to enamel.

A Halogen Bonding [2]Rotaxane Shuttle for Chloride-Selective Optical Sensing.

The first example of a [2]rotaxane shuttle capable of selective optical sensing of chloride anions over other halides is reported. The rotaxane was synthesised via a chloride ion template-directed cyclisation of an isophthalamide macrocycle around a multi-station axle containing peripheral naphthalene diimide (NDI) stations and a halogen bonding (XB) bis(iodotriazole) based station. Proton NMR studies indicate the macrocycle resides preferentially at the NDI stations in the free rotaxane, where it is stabilised by aromatic donor-acceptor charge transfer interactions between the axle NDI and macrocycle hydroquinone moieties. Addition of chloride ions in an aqueous-acetone solvent mixture induces macrocycle translocation to the XB anion binding station to facilitate the formation of convergent XB⋅⋅⋅Cl- and hydrogen bonding HB⋅⋅⋅Cl- interactions, which is accompanied by a reduction of the charge-transfer absorption band. Importantly, little to no optical response was induced by addition of bromide or iodide to the rotaxane, indicative of the size discriminative steric inaccessibility of the interlocked cavity to the larger halides, demonstrating the potential of using the mechanical bond effect as a potent strategy and tool in chloride-selective chemo-sensing applications in aqueous containing solvent environments.

Modular Synthesis of Improbable Rotaxanes with All‐Benzene Scaffolds

Abstract“Improbable” rotaxanes consisting of interlocked conjugated components represent non‐trivial synthetic targets, not to mention those with all‐benzene scaffolds. Herein, a modular synthetic strategy has been established using an isolable azo‐linked pre‐rotaxane as the core module, in which the azo group functions as a tracelessly removable template to direct mechanical bond formations. Through versatile connections of the pre‐rotaxane and other customizable modules, [2]‐ and [3]rotaxanes derived from all‐benzene scaffolds have been accomplished, demonstrating the utility and potential of the synthetic design for all‐benzene interlocked supramolecules.