Multiresponsive supramolecular gels constructed by orthogonal metal–ligand coordination and hydrogen bonding

Macromonomers bearing tridentate 2,6-bis(1,2,3-trizol-4-yl)pyridine (BTP) ligand unit synthesized via CuAAC “click” chemistry in the middle of the chain and two ureidopyrimidinone (UPy) motifs on the ends linked to the central BTP unit via PEGs of various lengths were synthesized and used for the study of gelation both with and without the presence of Eu(III) ions. Various interesting gelation behaviors were found. Gels exhibited various multi-responsive properties, including photoluminescence, mechanoresponsive properties, self-healing abilities, thermorepsonsive properties and chemoresponsive properties. The different gelation abilities and multi-responsive properties for different systems were shown to be resulted from difference in PEG linker lengths and the introduction of orthogonal metal–ligand coordination and hydrogen bonding interactions. The selective responsiveness to different chemicals would allow the development of modular sensory systems that utilize a combination of orthogonal supramolecular interactions.     

Supramolecular liquid-crystalline materials: molecular self-assembly and self-organization through intermolecular hydrogen bonding

Supramolecular liquid-crystals are molecular complexes formed from different and independent molecular species through specific molecular interactions such as hydrogen bonding. We have recently developed new types of H-bonded liquid-crystalline materials obtained by molecular self-assembly processes: (1) doubly H-bonded liquid-crystalline complexes through a molecular recognition process between 2,6-bis(acylamino)pyridines and benzoic acids, (2) liquid-crystalline polymer blends involving an H-bonding interaction between poly(4-vinylphenol) and a thermotropic main-chain polyester containing a lateral pyridyl substituent, (3) liquid-crystalline networks built through hydrogen bonds between multifunctional H-bonding components. These new materials may bridge a gap between liquid crystals and supramolecular systems.     

Hydrogen bonding and the self-assembly of supramolecular liquid-crystalline materials

Novel supramolecular liquid-crystalline materials have been obtained by the hydrogen bond formation between different and independent molecules. The self-assembly of carboxylic acid and pyridine moieties that function as H-bond donors and acceptors, respectively, results in the formation of mesogenic complex structures. A wide variety of liquid-crystalline low molecular weight complexes have been prepared using this approach. This concept has been extended to the polymeric systems. Hydrogen-bonded liquid-crystalline polymers that exhibit mesophases over wide temperature ranges, ferroelectricity or photo-responsibility have been prepared by the molecular association. Moreover, liquid-crystalline polymer networks that show reversible smectic-isotropic phase transitions have been formed by the hydrogen bonds. The dynamics of the hydrogen bonding may contribute to the induction of the mesomorphism of the networks.     

Transmembrane anion transport mediated by halogen bonding and hydrogen bonding triazole anionophores

Transmembrane ion transport by synthetic anionophores is typically achieved using polar hydrogen bonding anion receptors. Here we show that readily accessible halogen and hydrogen bonding 1,2,3-triazole derivatives can efficiently mediate anion transport across lipid bilayer membranes with unusual anti-Hofmeister selectivity. Importantly, the results demonstrate that the iodo-triazole systems exhibit the highest reported activity to date for halogen bonding anionophores, and enhanced transport efficiency relative to the hydrogen bonding analogues. In contrast, the analogous fluoro-triazole systems, which are unable to form intermolecular interactions with anions, are inactive. The halogen bonding anionophores also exhibit a remarkable intrinsic chloride over hydroxide selectivity, which is usually observed only in more complex anionophore designs, in contrast to the readily accessible acyclic systems reported here. This highlights the potential of iodo-triazoles as synthetically accessible and versatile motifs for developing more efficient anion transport systems. Computational studies provide further insight into the nature of the anion-triazole intermolecular interactions, examining the origins of the observed transport activity and selectivity of the systems, and revealing the role of enhanced charge delocalisation in the halogen bonding anion complexes.

Halogen and hydrogen bonding 1,2,3-triazole derivatives efficiently mediate anion transport across lipid bilayer membranes with unusual anion selectivity profiles.     

Au3-to-Ag3 coordinate-covalent bonding and other supramolecular interactions with covalent bonding strength

An efficient strategy for designing charge-transfer complexes using coinage metal cyclic trinuclear complexes (CTCs) is described herein. Due to opposite quadrupolar electrostatic contributions from metal ions and ligand substituents, [Au(μ-Pz-(i-C₃H₇)₂)]₃·[Ag(μ-Tz-(n-C₃F₇)₂)]₃ (Pz = pyrazolate, Tz = triazolate) has been obtained and its structure verified by single crystal X-ray diffraction – representing the 1^st crystallographically-verified stacked adduct of monovalent coinage metal CTCs. Abundant supramolecular interactions with aggregate covalent bonding strength arise from a combination of M–M′ (Au → Ag), metal–π, π–π interactions and hydrogen bonding in this charge-transfer complex, according to density functional theory analyses, yielding a computed binding energy of 66 kcal mol⁻¹ between the two trimer moieties – a large value for intermolecular interactions between adjacent d¹⁰ centres (nearly doubling the value for a recently-claimed Au(i) → Cu(i) polar-covalent bond: Proc. Natl. Acad. Sci. U.S.A., 2017, 114, E5042) – which becomes 87 kcal mol⁻¹ with benzene stacking. Surprisingly, DFT analysis suggests that: (a) some other literature precedents should have attained a stacked product akin to the one herein, with similar or even higher binding energy; and (b) a high overall intertrimer bonding energy by inferior electrostatic assistance, underscoring genuine orbital overlap between M and M′ frontier molecular orbitals in such polar-covalent M–M′ bonds in this family of molecules. The Au → Ag bonding is reminiscent of classical Werner-type coordinate-covalent bonds such as H₃N: → Ag in [Ag(NH₃)₂]⁺, as demonstrated herein quantitatively. Solid-state and molecular modeling illustrate electron flow from the π-basic gold trimer to the π-acidic silver trimer with augmented contributions from ligand-to-ligand’ (LL′CT) and metal-to-ligand (MLCT) charge transfer.

A stacked Ag₃–Au₃ bonded (66 kcal mol⁻¹) complex obtained crystallographically exhibits charge-transfer characteristics arising from multiple cooperative supramolecular interactions.     

Revealing the bonding of solvated Ru complexes with valence-to-core resonant inelastic X-ray scattering

Ru-complexes are widely studied because of their use in biological applications and photoconversion technologies. We reveal novel insights into the chemical bonding of a series of Ru(ii)- and Ru(iii)-complexes by leveraging recent advances in high-energy-resolution tender X-ray spectroscopy and theoretical calculations. We perform Ru 2p4d resonant inelastic X-ray scattering (RIXS) to probe the valence excitations in dilute solvated Ru-complexes. Combining these experiments with a newly developed theoretical approach based on time-dependent density functional theory, we assign the spectral features and quantify the metal–ligand bonding interactions. The valence-to-core RIXS features uniquely identify the metal-centered and charge transfer states and allow extracting the ligand-field splitting for all the complexes. The combined experimental and theoretical approach described here is shown to reliably characterize the ground and excited valence states of Ru complexes, and serve as a basis for future investigations of ruthenium, or other 4d metals active sites, in biological and chemical applications.

Combined experimental and theoretical Ru 2p4d resonant inelastic X-ray scattering study probes the chemical bonding and the valence excited states of solvated Ru complexes.     

Tuning energy landscapes and metal–metal interactions in supramolecular polymers regulated by coordination geometry

Herein, we exploit coordination geometry as a new tool to regulate the non-covalent interactions, photophysical properties and energy landscape of supramolecular polymers. To this end, we have designed two self-assembled Pt(ii) complexes 1 and 2 that feature an identical aromatic surface, but differ in the coordination and molecular geometry (linear vs. V-shaped) as a result of judicious ligand choice (monodentate pyridine vs. bidentate bipyridine). Even though both complexes form cooperative supramolecular polymers in methylcyclohexane, their supramolecular and photophysical behaviour differ significantly: while the high preorganization of the bipyridine-based complex 1 enables an H-type 1D stacking with short Pt⋯Pt contacts via a two-step consecutive process, the existence of increased steric effects for the pyridyl-based derivative 2 hinders the formation of metal–metal contacts and induces a single aggregation process into large bundles of fibers. Ultimately, this fine control of Pt⋯Pt distances leads to tuneable luminescence—red for 1vs. blue for 2, which highlights the relevance of coordination geometry for the development of functional supramolecular materials.

In this article, we exploit coordination geometry as a new tool to control the energy landscape and photophysical properties (red vs. blue luminescence) of supramolecular polymers.     

Observations of tetrel bonding between sp3-carbon and THF

We report the direct observation of tetrel bonding interactions between sp³-carbons of the supramolecular synthon 3,3-dimethyl-tetracyanocyclopropane (1) and tetrahydrofuran in the gas and crystalline phase. The intermolecular contact is established via σ-holes and is driven mainly by electrostatic forces. The complex manifests distinct binding geometries when captured in the crystalline phase and in the gas phase. We elucidate these binding trends using complementary gas phase quantum chemical calculations and find a total binding energy of −11.2 kcal mol⁻¹ for the adduct. Our observations pave the way for novel strategies to engineer sp³-C centred non-covalent bonding schemes for supramolecular chemistry.

sp³-C⋯THF tetrel bonding was observed in the crystalline state and in the gas phase. Density functional calculations revealed interaction energies up to −11.2 kcal mol⁻¹ and showed that these adducts are held together mainly by electrostatics.     

Supramolecular polymers fabricated by orthogonal self-assembly based on multiple hydrogen bonding and macrocyclic host–guest interactions

Supramolecular polymers constructed by orthogonal self-assembly based on multiple hydrogen bonding and macrocyclic host-guest interactions have received increasing attention due to their elegant structures,outstanding properties,and potential applications.Hydrogen bonding endows these supramolecular polymers with good adaptability and reversibility,while macrocyclic host-guest interactions give them good selectivity and versatile stimuli-responsiveness.Therefore,functional supramolecular polymers fabricated by these two highly specific,noninterfering interactions in an orthogonal way have shown wide applications in the fields of molecular machines,electronics,soft materials,etc.In this review,we discuss the recent advances of functional supramolecular polymers fabricated by orthogonal self-assembly based on multiple hydroge n bonding and host-guest interactions.In particular,we focus on crown ether-and pillar[n]arene-based supramolecular polymers due to their compatibility with multiple hydrogen bonds in organic solution.The fabrication strategies,interesting properties,and potential applications of these advanced supramolecular materials are mainly concerned.     

Halogen bonding in polymer science: towards new smart materials

The halogen bond is a special non-covalent interaction, which can represent a powerful tool in supramolecular chemistry. Although the halogen bond offers several advantages compared to the related hydrogen bond, it is currently still underrepresented in polymer science. The structural related hydrogen bonding assumes a leading position in polymer materials containing supramolecular interactions, clearly indicating the high potential of using halogen bonding for the design of polymeric materials. The current developments regarding halogen bonding containing polymers include self-assembly, photo-responsive materials, self-healing materials and others. These aspects are highlighted in the present perspective. Furthermore, a perspective on the future of this rising young research field is provided.

The incorporation of halogen bonding into polymer architectures is a new approach for the design of functional materials. This perspective emphasizes the current development in the field of halogen bonding featuring polymer materials.     

The remarkable role of hydrogen bond,halogen, and solvent effect on self-healing supramolecular gel

Self-healing supramolecular gels of low-molecular-weight (LMW) molecules are smart soft materials; however, the development of self-healing LMW gelator is still a challenging task because of the lack of in-depth studies about self-healing mechanisms of LMW gels and the solvent effect on gel properties. Therefore, herein a different perspective was used to study a family of D-gluconic acetal-based gelators with variable structural fragments in 14 different solvents, and a more detailed understanding of self-assembly and self-healing mechanism of supramolecular gels was attained. Based on the critical gelation concentration, phase transition temperature, and rheological data, A8 bearing an amide group in side chain and two chlorine atoms linked to benzene ring was found to be an outstanding gelator, which could form gels with good self-healing ability in a variety of solvents. Interestingly, A8 gel formed in n-BuOH demonstrates high transparency, good mechanical strength, self-supporting behavior, and great self-healing ability from mechanical damage. Based on the Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and theoretical calculation analysis, the self-assembly and self-healing mechanisms of A8 gel were proposed, indicating that a combination of hydrogen bonding and halogen effect was responsible for the efficient self-healing behavior of supramolecular gel. Furthermore, the analysis of solvent parameters indicated that the dispersion force of solvent favored gelators to self-assemble, hydrogen bonding donor ability of solvent mainly affected the formation of one-dimensional assembly, and hydrogen bonding receptor ability and polarity of solvent mainly influenced the supramolecular interactions among assemblies, significantly intervening the self-healing ability of gels. Overall, this study provides a new perspective to the understanding of gelator structure–property correlation in solvents and sheds light for future development of self-healing supramolecular gels.     

Molecular design of supramolecular polymers with chelated units and their application as functional materials

This article summarizes the basic concepts and synthetic strategies leading to various types of supramolecular polymers with chelated units, including linear, branched, cross-linked, and heterometallic polymers. Particular attention is paid to such new synthetic approaches to supramolecular polymers as hierarchical and orthogonal self-assembly based on a combination of metal–ligand interaction with hydrogen bonds and host–guest interactions. Metallosupramolecular polyelectrolytes, supramolecular polymer gels, self-assembled metallosupramolecular monolayers, and supramolecular metal chelate dendrimers are analyzed. The stimuli-responsive, self-healing, and shape memory supramolecular polymers with chelated units are considered. The bibliography includes articles published over the past five years.     

Deciphering the evolution of supramolecular nanofibers in solution and solid-state: a combined microscopic and spectroscopic approach

Supramolecular self-assembly of small organic molecules has emerged as a powerful tool to construct well-defined micro- and nanoarchitecture through fine-tuning a range of intermolecular interactions. The size, shape, and optical properties of these nanostructures largely depend on the specific assembly of the molecular building units, temperature and polarity of the medium, and external stimuli. The engineering of supramolecular self-assembled nanostructures with morphology-dependent tunable emission is in high demand due to the promising scope in nanodevices and molecular machines. However, probing the evolution of molecular aggregates from the solution and directing the self-assembly process in a pre-defined fashion are challenging. In the present study, we have deciphered the sequential evolution of supramolecular nanofibers from solution to spherical and oblong-shaped nanoparticles through the variation of solvent polarity, tuning the hydrophobic–hydrophilic interactions. An intriguing case of molecular self-assembly has been elucidated employing a newly designed π-conjugated thiophene derivative (TPAn) through a combination of steady-state absorption, emission measurements, fluorescence correlation spectroscopy (FCS), and electron microscopy. The FCS analysis and microscopy results revealed that the small-sized nanofibers in the dispersion further agglomerated upon solvent evaporation, resulting in a network of nanofibers. Stimuli-responsive reversible interconversion between a network of nanofibers and spherical nanoaggregates was probed both in dispersion and solvent-evaporated state. The evolution of organic nanofibers and a subtle control over the self-assembly process demonstrated in the current investigation provide a general paradigm to correlate the size, shape, and emission properties of fluorescent molecular aggregates in complex heterogeneous media, including a human cell.

Supramolecular nanofiber evolution in solution and solid-state, including stimuli-responsive reversible interconversion among diverse nanoarchitectures, was probed through a combined spectroscopic and microscopic approach.     

Controllable DNA strand displacement by independent metal–ligand complexation

Introduction of artificial metal–ligand base pairs can enrich the structural diversity and functional controllability of nucleic acids. In this work, we revealed a novel approach by placing a ligand-type nucleoside as an independent toehold to control DNA strand-displacement reactions based on metal–ligand complexation. This metal-mediated artificial base pair could initiate strand invasion similar to the natural toehold DNA, but exhibited flexible controllability to manipulate the dynamics of strand displacement that was only governed by its intrinsic coordination properties. External factors that influence the intrinsic properties of metal–ligand complexation, including metal species, metal concentrations and pH conditions, could be utilized to regulate the strand dynamics. Reversible control of DNA strand-displacement reactions was also achieved through combination of the metal-mediated artificial base pair with the conventional toehold-mediated strand exchange by cyclical treatments of the metal ion and the chelating reagent. Unlike previous studies of embedded metal-mediated base pairs within natural base pairs, this metal–ligand complexation is not integrated into the nucleic acid structure, but functions as an independent toehold to regulate strand displacement, which would open a new door for the development of versatile dynamic DNA nanotechnologies.

This metal-mediated artificial base pair can function as an independent toehold based on metal–ligand coordination and exhibit flexible and reversible controllability to manipulate the dynamics of strand displacement.     

Metallohelices emulate the properties of short cationic α-helical peptides

Naturally occurring peptides in many living systems perform antimicrobial and anticancer host defence roles, but their potential for clinical application is limited by low metabolic stability and relatively high costs of goods. Self-assembled helical metal complexes provide an attractive synthetic platform for non-peptidic architectures that can emulate some of the properties of short cationic α-helical peptides, with tuneable charge, shape, size and amphipathicity. Correspondingly there is a growing body of evidence demonstrating that these supramolecular architectures exhibit bioactivity that emulates that of the natural systems. We review that evidence in the context of synthetic advances in the area, driven by the potential for biomedical applications. We note some design considerations for new biologically-relevant metallohelices, and give our outlook on the future of these compounds as therapeutic peptidomimetics.

Advances in metal–organic self-assembly have unearthed an area of chemical space containing peptide-emulating molecules. Comparison with natural systems indicates future directions in terms of synthesis, disease areas and mechanistic understanding.     

High modulus ratio shape‐memory polymers achieved by combining hydrogen bonding with controlled crosslinking

A new type of poly(methyl acrylate)‐co‐(acrylic acid) (PMA‐AA) networks obtained by combining hydrogen bonding with controlled crosslinking exhibit full and rapid shape‐memory recovery. The structure, thermal properties, dynamical mechanical properties and shape‐memory effects of these networks were presented. High modulus ratios were achieved for the series of PMA‐AA networks based on intense self‐complementary hydrogen bonding in poly(acrylic acid) (PAA) segments. This lead to excellent shape‐memory effects with strain‐recovery ratio above 99%. Meanwhile, faster recovery speed was achieved by the synergistic effect of hydrogen bonding and controlled crosslinking compared to the linear PMA‐AA copolymers. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1241–1245, 2011     

Reversible OH-bond activation and amphoterism by metal–ligand cooperativity of calix[4]pyrrolato aluminate

Most p-block metal amides irreversibly react with metal alkoxides when subjected to alcohols, making reversible transformations with OH-substrates a challenging task. Herein, we describe how the combination of a Lewis acidic square-planar-coordinated aluminum(iii) center with metal–ligand cooperativity leverages unconventional reactivity toward protic substrates. Calix[4]pyrrolato aluminate performs OH-bond activation of primary, secondary, and tertiary aliphatic and aromatic alcohols, which can be fully reversed under reduced pressure. The products exhibit a new form of metal–ligand cooperative amphoterism and undergo counterintuitive substitution reactions of a polar covalent Al–O bond by a dative Al–N bond. A comprehensive mechanistic picture of all processes is buttressed by isolation of intermediates, spectroscopy, and computation. This study delineates how structural constraints can invert thermodynamics for seemingly simple addition reactions and invert common trends in bond energies.

The combination of structural constraint and metal–ligand cooperativity in calix[4]pyrrolato aluminate inverts common trends of bond energies and enables reversible OH-bond activation.     

N-Oxide S–O chalcogen bonding in conjugated materials

Non-covalent bonding interactions, such as chalcogen bonding, can have a substantial effect on the electronic and physical properties of conjugated polymers and is largely dependent on the strength of interaction. Functional groups that are traditionally used to instill chalcogen bonding such as alkoxy or fluorine substituents can demand challenging synthetic effort, as well as have drastic effects on the electronics of a π-system. The incorporation of a N-oxide functionality into bithiazole-containing materials, a synthetically simple transformation, has been entirely overlooked until now. A systematic analysis of the effects of N-oxidation on the electronic and physical properties of bithiazole-containing materials has been undertaken. N-Oxidation has been found to affect the electronic band gap through increase of the HOMO and lowering of the LUMO. Furthermore, exceptionally strong intramolecular S–O chalcogen bonding interactions in the bithiazole core contribute to rigidification of the conjugated system. Computational analysis of this system has shown this N-oxide chalcogen bonding interaction to be significantly stronger than other chalcogen bonding interactions commonly exploited in conjugated materials.

N-Oxide incorporation into thiazole-containing conjugated materials can have substantial effects on both the electronic and physical properties. A notably strong non-covalent S–O interaction is observed between the N-oxide and neighbouring sulfur.     

Ground- and excited-state dynamic control of an anion receptor by hydrostatic pressure

Stimulus-responsive supramolecular architectures have become an attractive alternative to conventional ones for many applications in sensing, drug-delivery and switchable memory systems. Herein, we used an anion receptor (H: host) as a hydrostatic-pressure-manipulatable fluorescence foldamer and halide anions as chiral (binaphthylammonium) and achiral (tetrabutylammonium) ion pairs (SS or RR·X and TBA·X; X = Cl, Br), and then investigated their (chir)optical properties and molecular recognition behavior under hydrostatic pressures. The conformational changes and optical properties of H in various organic solvents were revealed by UV/vis absorption and fluorescence spectra and fluorescence lifetimes upon hydrostatic pressurization. The anion-recognition abilities of H upon interactions with SS or RR·X and TBA·X at different pressure ranges were determined by hydrostatic-pressure spectroscopy to quantitatively afford the binding constant (K_anion) and apparent reaction volume changes . The results obtained indicate that hydrostatic pressure as well as solvation plays significant roles in the dynamic control of the present supramolecular system in the ground and excited states. This work will provide a new guideline for further developing hydrostatic-pressure-responsive foldamers and supramolecular materials.

Hydrostatic pressure can control interactions of chiral countercations with helical receptors containing anions, causing remarkable chiroptical changes.     

Towards photoswitchable quadruple hydrogen bonds via a reversible “photolocking” strategy for photocontrolled self-assembly

Developing new photoswitchable noncovalent interaction motifs with controllable bonding affinity is crucial for the construction of photoresponsive supramolecular systems and materials. Here we describe a unique “photolocking” strategy for realizing photoswitchable control of quadruple hydrogen-bonding interactions on the basis of modifying the ureidopyrimidinone (UPy) module with an ortho-ester substituted azobenzene unit as the “photo-lock”. Upon light irradiation, the obtained Azo-UPy motif is capable of unlocking/locking the partial H-bonding sites of the UPy unit, leading to photoswitching between homo- and heteroquadruple hydrogen-bonded dimers, which has been further applied for the fabrication of novel tunable hydrogen bonded supramolecular systems. This “photolocking” strategy appears to be broadly applicable in the rational design and construction of other H-bonding motifs with sufficiently photoswitchable noncovalent interactions.

A photolocking strategy is described to achieve the construction of effectively photoswitchable quadruple hydrogen bonds featuring with photoregulable H-bonding affinities, which is further applied in the photocontrollable H-bonded self-assemblies.