Functional Supramolecular Materials Research Articles

Hierarchical H-bonding and metal coordination bonds enabled supramolecular dual networks for high-performance energy-dissipation

Natural organisms have superior material properties such as mechanical adaptability, impact protection, and self-healing to protect the body from complicated external environments, fascinating the development of functional supramolecular elastic materials with biomimetic protective features. Herein, a dual physically crosslinked supramolecular polyurethane (PU) network with strain-hardening effect is synthesized by incorporating hierarchical hydrogen bonds (H-bond) and metal coordination bonds into an elastomer matrix. A moderate content of quadruple H-bonds is critical for achieving a prominent toughness and a considerable strain-at-break owing to the strain hardening effect enabled by the hierarchical H-bonds. When the Zn-to-pyridine coordination bonds were introduced to the supramolecular PU, the strength, toughness, and energy dissipation properties were further enhanced attributing to the dual physical crosslinking networks. The dynamic dissociation and association of the sacrificial H-bonds and Zn-to-pyridine coordination bonds induced significant strain hardening effect and enabled tremendous energy absorption and self-healing properties. Besides, the supramolecular PU elastomers and their blends were foamed via scCO2 foaming to produce supramolecular foams containing dynamic bonds. The composite foam could effectively reduce the impact force from 6085 N to 373 N and achieve an outstanding energy absorption efficiency of 93.87% owing to the synergistic effect of porous structure and dual physically crosslinked networks. This work provides an innovative strategy for designing high-performance energy absorbing supramolecular elastomers and cushioning foams with reversible bonds.

Tetraphenylethyelne (TPE)-Based Macrocycles Exhibiting (anti) Aromaticity

I will present the synthesis of four-, six- and eight-membered tetraphenylethylene (TPE)-based macrocycles on Ag(111) via on-surface Ullmann coupling reactions. Their unique chemical and physical properties, such as intrinsic inner cavities and aromaticity/antiaromaticity make these systems appealing building blocks for functional supramolecular materials. The as-synthesized macrocycles are spontaneously segregated on the surface and self-assemble as large-area two-dimensional mono-component supramolecular crystals. Combined in-situ characterized by scanning tunneling spectroscopic and computational analysis evidence that the macrocycles undergo structural and orbital symmetry breaking due to extended conjugation in the macrocycles.

Halogen Bond-Assisted Supramolecular Dimerization of Pyridinium-Fused 1,2,4-Selenadiazoles via Four-Center Se2N2 Chalcogen Bonding.

The synthesis and structural characterization of α-haloalkyl-substituted pyridinium-fused 1,2,4-selenadiazoles with various counterions is reported herein, demonstrating a strategy for directed supramolecular dimerization in the solid state. The compounds were obtained through a recently discovered 1,3-dipolar cycloaddition reaction between nitriles and bifunctional 2-pyridylselenyl reagents, and their structures were confirmed by the X-ray crystallography. α-Haloalkyl-substituted pyridinium-fused 1,2,4-selenadiazoles exclusively formed supramolecular dimers via four-center Se···N chalcogen bonding, supported by additional halogen bonding involving α-haloalkyl substituents. The introduction of halogens at the α-position of the substituent R in the selenadiazole core proved effective in promoting supramolecular dimerization, which was unaffected by variation of counterions. Additionally, the impact of cocrystallization with a classical halogen bond donor C6F3I3 on the supramolecular assembly was investigated. Non-covalent interactions were studied using density functional theory calculations and topological analysis of the electron density distribution, which indicated that all ChB, XB and HB interactions are purely non-covalent and attractive in nature. This study underscores the potential of halogen and chalcogen bonding in directing the self-assembly of functional supramolecular materials employing 1,2,4-selenadiazoles derived from recently discovered cycloaddition between nitriles and bifunctional 2-pyridylselenyl reagents.

Oligo(phenyleneethynylene)s: Shape-Tunable Building Blocks for Supramolecular Self-Assembly.

Oligo(phenyleneethynylene)s (OPEs) have attracted widespread attention due to their remarkable (opto)electronic and photophysical properties, which have enabled numerous applications. The versatile functionalization possibilities of OPEs make them unique candidates to form various shape-persistent geometries, including linear, triangular, rectangular, hexagonal and macrocyclic. However, as a result of this structural variety, it is oftentimes challenging to correlate molecular design with self-assembly properties. In this minireview, we have classified OPEs based on their molecular shapes and correlated them with their self-assembly behavior in solution. Particularly, we provide important insights into the aggregation propensity of the different molecular shapes and how to tune the association strength using various non-covalent interactions. Our classification will enable a better understanding of the structure-property correlation in OPEs, which is key to develop supramolecular functional materials.

Oligo(phenyleneethynylene)s: Shape‐Tunable Building Blocks for Supramolecular Self‐Assembly

AbstractOligo(phenyleneethynylene)s (OPEs) have attracted widespread attention due to their remarkable (opto)electronic and photophysical properties, which have enabled numerous applications. The versatile functionalization possibilities of OPEs make them unique candidates to form various shape‐persistent geometries, including linear, triangular, rectangular, hexagonal and macrocyclic. However, as a result of this structural variety, it is oftentimes challenging to correlate molecular design with self‐assembly properties. In this minireview, we have classified OPEs based on their molecular shapes and correlated them with their self‐assembly behavior in solution. Particularly, we provide important insights into the aggregation propensity of the different molecular shapes and how to tune the association strength using various non‐covalent interactions. Our classification will enable a better understanding of the structure‐property correlation in OPEs, which is key to develop supramolecular functional materials.

Macrocyclic Diacetylene / Sulfonate Fluorophore Hierarchical Multifunctional Nanotoroids.

Functional supramolecular materials exhibit important features including structural versatility and versatile applications. Here, this study reports the construction of unique hierarchically organized nanotoroids exhibiting fluorescence, photocatalytic, and sensing properties. The nanotoroids comprise of macrocyclic diacetylenes (MCDA) and 8-anilino-1-naphthalene sulfonate (ANS), a negatively charged aromatic fluorescent dye. This study shows that the hierarchical structure of the nanotoroids consist of MCDA nanofibers formed by stacked diacetylene monomers as the basic units, which are further bent and aligned into toroidal organization by electrostatic and hydrophobic interactions with the ANS molecules. The amine moieties on the nanotoroids surface are employed for deposition of gold nanostructures - Au nanoparticles or Au nanosheets - which constitute effective platforms for photocatalysis and surface enhanced Raman scattering (SERS)-based sensing.

Supramolecular Chemistry of Sumanene

AbstractSumanene is a buckybowl molecule that is continuously attracting the attention of the scientific community because of its unique geometrical and physicochemical properties. This Minireview systematically summarizes advances and considerations regarding the applied supramolecular chemistry of sumanene. This work highlights the major fields in which potential or real applications of sumanene molecule have been reported to date, such as the design of sumanene‐containing functional supramolecular materials and architectures, sumanene‐based drug‐delivery systems, or sumanene‐tethered ion‐selective molecular receptors. An assessment of the current status in the applied supramolecular chemistry of sumanene is provided, together with an emphasis on the key advances being made. Discussion on those milestones that are still to be achieved within this emerging field is also provided.

Supramolecular Chemistry of Sumanene.

Sumanene is a buckybowl molecule that is continuously attracting the attention of the scientific community because of its unique geometrical and physicochemical properties. This Minireview systematically summarizes advances and considerations regarding the applied supramolecular chemistry of sumanene. This work highlights the major fields in which potential or real applications of sumanene molecule have been reported to date, such as the design of sumanene-containing functional supramolecular materials and architectures, sumanene-based drug-delivery systems, or sumanene-tethered ion-selective molecular receptors. An assessment of the current status in the applied supramolecular chemistry of sumanene is provided, together with an emphasis on the key advances being made. Discussion on those milestones that are still to be achieved within this emerging field is also provided.

Computational Design of Peptide Assemblies.

With the ongoing development of peptide self-assembling materials, there is growing interest in exploring novel functional peptide sequences. From short peptides to long polypeptides, as the functionality increases, the sequence space is also expanding exponentially. Consequently, attempting to explore all functional sequences comprehensively through experience and experiments alone has become impractical. By utilizing computational methods, especially artificial intelligence enhanced molecular dynamics (MD) simulation and de novo peptide design, there has been a significant expansion in the exploration of sequence space. Through these methods, a variety of supramolecular functional materials, including fibers, two-dimensional arrays, nanocages, etc., have been designed by meticulously controlling the inter- and intramolecular interactions. In this review, we first provide a brief overview of the current main computational methods and then focus on the computational design methods for various self-assembled peptide materials. Additionally, we introduce some representative protein self-assemblies to offer guidance for the design of self-assembling peptides.

Creating Supramolecular Functional Materials via Nucleobase Interaction: Investigating Molecular Recognition and the Fabrication of Surface Relief Gratings

Creating Supramolecular Functional Materials via Nucleobase Interaction: Investigating Molecular Recognition and the Fabrication of Surface Relief Gratings

Supramolecular macrocycles-based functional materials for the detection and adsorption of PFASs pollutant in water

Supramolecular macrocycles-based functional materials for the detection and adsorption of PFASs pollutant in water

Anisotropic ion-conductive supramolecular columnar liquid crystals composed of a benzonitrile derivative and ionic liquids

Self-organized liquid-crystalline (LC) electrolytes, which feature externally controllable ion channels, are at the forefront of advanced materials for developing next generation batteries and actuators. In this study, we present a novel family of supramolecular columnar liquid crystals that exhibit anisotropic ion-conducting properties. These liquid crystals are formed by self-assembly of a taper-shaped benzonitrile derivative with an amide moiety and ionic liquids (1-ethyl-3-methylimidazolium bromide and 1-butyl-3-methylimidazolium bromide). The cooperative interactions between the nitrile dipole-ion interaction and the bromide anion–amide NH hydrogen bond effectively confine ionic liquids to the center of columns, forming one-dimensional channels. By applying a shearing force, we achieved a uniform horizontal orientation of the supramolecular columns between comb-shaped gold electrodes deposited on a glass substrate. The columnar LC complexes that contained larger cations exhibited higher ionic conductivities compared to those with smaller cations. This can be attributed to the effective ion dissociation resulting from weak Coulombic interactions caused by the larger size of the ionic liquid, as well as the attractive cation-dipole interaction. The present study not only contributes to the understanding of the interplay of noncovalent forces but also offers insights for the design of functional supramolecular materials for future ionic devices.

Crown‐Ether‐Ring Size Dependent Crystal Structures, Phase Transition and Dielectric Properties of [M(crown)]BF4⋅xH2O (M+=Na+, K+; crown=15‐crown‐5, 18‐crown‐6; x=0 or 1)

AbstractCrown ethers demonstrate significant conformational flexibility and rotational symmetry, rendering them invaluable in the realms of supramolecular chemistry and crystal engineering. These unique natures facilitate the construction of supramolecular crystals of crown ethers, characterized by disorder‐order phase transitions, imparts unique properties that hold promise for diverse applications across multiple fields. In this study, four supramolecular compounds, namely [Na(15‐crown‐5)]BF4 (1), [Na(18‐crown‐6)]BF4⋅H2O (2), [K(15‐crown‐5)]BF4 (3) and [K(18‐crown‐6)]BF4⋅H2O (4) were synthesized and characterized by microanalysis, thermogravimetric analysis, differential scanning calorimetry and powder X‐ray diffraction techniques. Herein, 15‐crown‐5 and 18‐crown‐6 correspond to 1,4,7,10,13‐pentaoxacyclopentadecane and 1,4,7,10,13,16‐hexaoxacyclooctadecane, respectively. It was observed that the crystal structure, phase transition, and dielectric properties of these supramolecular compounds are significantly influenced by the size of the crown‐ether rings. The research extensively discussed the correlation between the coordination mode of metal ions of K+ or Na+ with crown ethers, the compatibility between metal ions and crown‐ether rings in terms of size, and the effects of crown‐ether disorder on dielectric permittivity during phase transitions. Our discoveries hold significant implications for the design and development of crown‐ether supramolecular functional materials.

Manipulating the optimal transport orbital and virtual states in a supramolecular transistor

Supramolecular electronics bridges the gap between single-molecule electronics and bulk, plastic electronics, and is embodied as one of the biggest promises of nanometer electronics made by supramolecular functional materials. Within this field, the way in which electrons propagate through the supramolecule plays a profound role both in designing supramolecular devices and in understanding the structure–property relationships at the molecular level. Herein, we consider a supramolecular transistor, which contains bipartite molecular monomers, with one molecular orbital is non-interacting, whereas the other one is strongly correlated. Modeling this device using the two-impurity Anderson model, we unravel the orbital selections and the virtual states in the electronic transport process with the aid of the celebrated numerical renormalization group method. We demonstrate that if both orbitals are in their particle-hole symmetric regimes, electrons favor to transmit through the non-interacting molecular orbital via the resonant tunneling process, rather than through the strongly correlated molecular orbital via the Kondo effect, despite the energy of the strongly correlated orbital is lower. This phenomenon indicates that if the Kondo effect occurs, it experiences a temporarily doubly occupied virtual state. Interestingly, the situation reverses if the inter-molecule hopping integral is applied, where the strongly correlated orbital becomes optimal and the virtual state turns to be an empty state. To understand these behaviors, both the static and the dynamical properties, as well as those thermodynamic quantities are studied in detail, and necessary physical arguments are given. Our findings afford deep insights into the manipulations of the optimal transport orbital and the Kondo behaviors within quantum impurity devices.

Confinement inside MOFs Enables Guest-Modulated Spin Crossover of Otherwise Low-Spin Coordination Cages.

Confinement of discrete coordination cages within nanoporous lattices is an intriguing strategy to gain unusual properties and functions. We demonstrate here that the confinement of coordination cages within metal-organic frameworks (MOFs) allows the spin state of the cages to be regulated through multilevel host-guest interactions. In particular, the confined in situ self-assembly of an anionic FeII4L6 nanocage within the mesoporous cationic framework of MIL-101 leads to the ionic MOF with an unusual hierarchical host-guest structure. While the nanocage in solution and in the solid state has been known to be invariantly diamagnetic with low-spin FeII, FeII4L6@MIL-101 exhibits spin-crossover (SCO) behavior in response to temperature and release/uptake of water guest within the MOF. The distinct color change concomitant with water-induced SCO enables the use of the material for highly selective colorimetric sensing of humidity. Moreover, the spin state and the SCO behavior can be modulated also by inclusion of a guest into the hydrophobic cavity of the confined cage. This is an essential demonstration of the phenomenon that the confinement within porous solids enables an SCO-inactive cage to show modulable SCO behaviors, opening perspectives for developing functional supramolecular materials through hierarchical host-guest structures.

Controlling Helical Asymmetry in Supramolecular Copolymers by In Situ Chemical Modification.

Amplification of asymmetry in complex molecular systems results from a delicate interplay of chiral supramolecular structures and their chemical reactivity. In this work, we show how the helicity of supramolecular assemblies can be controlled by performing a non-stereoselective methylation reaction on comonomers. By methylating chiral glutamic acid side chains in benzene-1,3,5-tricarboxamide (BTA) derivatives to form methyl esters, the assembly properties are modulated. As reacted comonomers, the methyl ester-BTAs induce a stronger bias in the screw-sense of helical fibers predominantly composed of stacked achiral alkyl-BTA monomers. Hence, applying the in situ methylation in a system with the glutamic acid-BTA comonomer induces asymmetry amplification. Moreover, mixing small quantities of enantiomers of glutamic acid-BTA and glutamate methyl ester-BTA in the presence of the achiral alkyl-BTAs leads to deracemization and inversion of the helical structures in solution via the in situ reaction toward a thermodynamic equilibrium. Theoretical modeling suggests that the observed effects are caused by enhanced comonomer interactions after the chemical modification. Our presented methodology enables on-demand control over asymmetry in ordered functional supramolecular materials.

Peptide Assembly of Different Dimensions and Their Effect on Myoblast Proliferation.

Variations in the functionalities of materials of different dimensions containing the same functional groups can be attributed to the structural stability and morphology of the materials. The morphology of peptide assemblies can influence their interactions with biological systems and ultimately modulate their bioactivity. Among reported Arg-Gly-Asp (RGD)-based supramolecular materials, two-dimensional (2-D) peptide assembly has been rarely studied. Herein, we report the fabrication of RGD-based supramolecular one-dimensional (1-D) and 2-D assemblies as peptide-based myoblast growth accelerators. The 2-D assembly was more effective in proliferating C2C12 cells than the 1-D assembly. These findings provide insights into the construction of optimal RGD-based supramolecular functional materials of different dimensions.

Triphenylamine-Functionalized Coordination Cage as a Supramolecular Fluorescence Sensor for Sequential Detection of Aluminum Ions and Nitrofurantoin.

Coordination cages with a well-defined nanocavity are a class of promising supramolecular materials for molecular recognition and sensing. However, their applications in sequential sensing of multiple types of pollutants are highly desirable yet extremely limiting and challenging. Herein, we demonstrate a convenient strategy to develop a supramolecular fluorescence sensor for sequentially detecting environmental pollutants of aluminum ions and nitrofurantoin. A coordination cage (Ni-NTB), adopting an octahedral structure with triphenylamine chromophores occupying on the faces, is weakly emissive in solution due to the intramolecular rotations of the phenyl rings. Ni-NTB exhibits sensitive and selective fluorescence "off-on-off" processes during consecutive sensing of Al3+ and nitrofurantoin, an antibacterial drug. These sequential detection processes are highly interference-tolerant and visually observable with the naked eye. Mechanism studies reveal that the fluorescence switch is controllable by tuning the degree of intramolecular rotations of the phenyl rings and the pathway of intermolecular charge transfer, which is associated with the host-guest interaction. Moreover, the fabrication of Ni-NTB on test strips enabled a quick naked-eye sequential sensing of Al3+ and nitrofurantoin in seconds. Hence, this novel supramolecular fluorescence "off-on-off" sensing platform provides a new approach to developing supramolecular functional materials for monitoring environmental pollution.

On-surface synthesis and spontaneous segregation of conjugated tetraphenylethylene macrocycles

Creating conjugated macrocycles has attracted extensive research interest because their unique chemical and physical properties, such as conformational flexibility, intrinsic inner cavities and aromaticity/antiaromaticity, make these systems appealing building blocks for functional supramolecular materials. Here, we report the synthesis of four-, six- and eight-membered tetraphenylethylene (TPE)-based macrocycles on Ag(111) via on-surface Ullmann coupling reactions. The as-synthesized macrocycles are spontaneously segregated on the surface and self-assemble as large-area two-dimensional mono-component supramolecular crystals, as characterized by scanning tunneling microscopy (STM). We propose that the synthesis benefits from the conformational flexibility of the TPE backbone in distinctive multi-step reaction pathways. This study opens up opportunities for exploring the photophysical properties of TPE-based macrocycles.

Macroscopic Supramolecular Assembly of Rigid Building Blocks Facilitated by Layer-By-Layer Assembled Microgel Film

Macroscopic supramolecular assembly (MSA) of building blocks larger than 1 μm provides new methodology for fabrication of functional supramolecular materials and a platform for mechanism investigation of interfacial phenomena. Most reports on MSA are restricted to soft hydrogels, and supramolecular groups can be directly integrated into a hydrogel matrix to generate sufficient attraction for maintaining macroscopic assemblies. For non-hydrogel stiff building blocks, two layer-by-layer modification processes consisting of flexible spacing coating and additional interacting groups are necessary to enable MSA, which is laborious and time-consuming. Approaches for highly efficient MSA based on flexible spacing coating are desired. In this work, MSA of polydimethylsiloxane (PDMS) building blocks is demonstrated by inducing microgel films that serve as both flexible spacing coating and surface functional groups, thus avoiding a two-step LbL modification process. By the varying bilayer number of microgel films, the MSA probability of modified PDMS increases from 54% at 3 bilayers to 100% at 6 bilayers. Control experiments and in situ force measurement strongly support the obtained MSA results and verify the dominant role of the microgel film as a flexible spacing coating and a supramolecularly interactive layer in achieving MSA. Moreover, the underlying mechanism is interpreted as low Young's modulus microgel films rendering surface groups highly mobile to enhance the multivalent interfacial binding. Taken together, this work has demonstrated the feasibility of MSA of rigid building blocks assisted by microgel films as flexible spacing coating and supramolecularly interactive layer simultaneously, which may extend the application fields of microgel materials to interfacial adhesion and advanced manufacturing with MSA methodology.