Recent Developments in Polymeric Assemblies and Functional Materials by Halogen Bonding

ConspectusSince its inception in the early 1990s, the field of supramolecular polymers (SPs) has grown into an interdisciplinary field of chemistry. It expanded from the self-assembly of molecular building blocks based on H-bonding into the realm of complex dynamic material, encompassing both supramolecular noncovalent and molecular covalent regimes. It has paved the path for a more diverse field of research into a new class of polymeric materials, coined dynamic polymers or dynamers. Dynamers are bringing a paradigm shift not only in material science research but also in a broad field of applications from self-healing materials to biocompatible polymeric materials. The present Account presents the evolution of supramolecular polymer chemistry from simple linear polymeric chains to complex dynamic polymers imparting novel functional properties, such as component exchange and self-healing. We explore how SPs led to materials of increasing complexity, starting from simple main-chain polymers to the formation of more complex columnar SPs and lateral SPs. The field has experienced three partially overlapping periods. The main goal was first the generation of polymeric entities from various molecular components connected through noncovalent interactions, especially complementary hydrogen bonding recognition patterns as well as stacked columnar SPs. Thereafter, attention was directed in parallel to the exploration of the properties of SPs and their applications as novel materials. In a third period, the dynamic properties of supramolecular polymers were explored, taking advantage of the lability of noncovalent interactions to perform component rearrangement and exchange. We illustrate how the field of SPs has emerged as a multidisciplinary field of chemistry, biology, and materials science with selected examples from the literature. The SPs, specifically dynamic owing to their inherent reversibility, also pave the path to easier sorting and recycling, as desired in the plastics industry.One of the biggest challenges that the plastics industry is facing today is the end-of-life fate of plastics. Plastics that cannot be recycled end up in landfills or are improperly disposed of in rivers and oceans, polluting and damaging the environmental balance irreversibly. Dynamic polymeric materials presenting inherent dynamicity could pave the way for addressing this long-standing challenge of nonrecyclability of plastics. Dynamers formed via noncovalent interactions or reversible covalent bonds can be broken into components that could be easily recycled and reused. Therefore, dynamers could play a pivotal role toward closing the loop for the plastics industry and provide a solution to an elusive circular economy with plastics being an integral part.

Owing to the mastery exhibited by Nature in integrating both covalent and noncovalent interactions in a highly efficient manner, the quest to construct polymeric systems that rival not only the precision and fidelity but also the structure of natural systems has remained a daunting challenge. Supramolecular chemists have long endeavored to control the interplay between covalent and noncovalent bond formation, so as to examine and fully comprehend how function is predicated on self-assembly. The ability to reliably control polymer self-assembly is essential to generate "smart" materials and has the potential to tailor polymer properties (i.e., viscosity, electronic properties) through fine-tuning the noncovalent interactions that comprise the polymer architecture. In this context, supramolecular polymers have a distinct advantage over fully covalent systems in that they are dynamically modular, since noncovalent recognition motifs can be engineered to either impart a desired functionality within the overall architecture or provide a designed bias for the self-assembly process. In this Account, we describe engineering principles being developed and pursued by our group that exploit the orthogonal nature of noncovalent interactions, such as hydrogen bonding, metal coordination, and Coulombic interactions, to direct the self-assembly of functionalized macromolecules, resulting in the formation of supramolecular polymers. To begin, we describe our efforts to fabricate a modular poly(norbornene)-based scaffold via ring-opening metathesis polymerization (ROMP), wherein pendant molecular recognition elements based upon nucleobase-mimicking elements (e.g., thymine, diaminotriazine) or SCS-Pd(II) pincer were integrated within covalent monofunctional or symmetrically functionalized polymers. The simple polymer backbones exhibited reliable self-assembly with complementary polymers or small molecules. Within these systems, we applied successful protecting group strategies and template polymerizations to enhance the control afforded by ROMP. Main-chain-functionalized alternating block polymers based upon SCS-Pd(II) pincer-pyridine motifs were achieved through the combined exploitation of bimetallic initiators and supramolecularly functionalized terminators. Our initial design principles led to the successful fabrication of both main-chain- and side-chain-functionalized poly(norbornenes) via ROMP. Utilizing all of these techniques in concert led to engineering orthogonality while achieving complexity through the installation of multiple supramolecular motifs within the side chain, main chain, or both in our polymer systems. The exploitation and modification of design principles based upon functional ROMP initiators and terminators has resulted in the first synthesis of main-chain heterotelechelic polymers that self-assemble into A/B/C supramolecular triblock polymers composed of orthogonal cyanuric acid-Hamilton wedge and SCS-Pd(II) pincer-pyridine motifs. Furthermore, supramolecular A/B/A triblock copolymers were realized through the amalgamation of functionalized monomers, ROMP initiators, and terminators. To date, this ROMP-fabricated system represents the only known method to afford polymer main chains and side chains studded with orthogonal motifs. We end by discussing the impetus to attain functional materials via orthogonal self-assembly. Collectively, our studies suggest that combining covalent and noncovalent bonds in a well-defined and precise manner is an essential design element to achieve complex architectures. The results discussed in this Account illustrate the finesse associated with engineering orthogonal interactions within supramolecular systems and are considered essential steps toward developing complex biomimetic materials with high precision and fidelity.

Inspired by the vast array of assemblies present in nature, supramolecular chemistry has attracted significant attention on account of its diverse supra-structures, which include micelles, vesicles, and fibers, in addition to its extensive applications in luminescent materials, sensors, bioimaging, and drug delivery over the past decades. Supramolecular polymers, which represent a combination of supramolecular chemistry and polymer science, are constructed by non-covalent interactions, such as host-guest interactions, hydrogen bonding, hydrophobic or hydrophilic interactions, metal-ligand interactions, π-π stacking, and electrostatic interactions. To date, numerous host-guest recognition systems have been reported, including crown ethers, cyclodextrins, calixarenes, cucurbituril, pillararenes, and other macrocyclic hosts. Among them, crown ethers, as the first generation of macrocyclic hosts, provide a promising and facile alternative route to supramolecular polymers. In addition, the incorporation of fluorophores into supramolecular polymers could endow them with multiple properties and functions, thereby presenting potential advantages in the context of smart materials. Thus, this review focuses on the fabrication strategies, interesting properties, and potential applications of fluorescent supramolecular polymers based on crown ethers. Typical examples are presented and discussed in terms of three different types of building blocks, namely covalently bonded low-molecular-weight compounds, polymers modified by hosts or guests, and supramolecular coordination complexes.

Dynamic DNA-based circuits represent versatile systems to perform complex computing operations at the molecular level. However, the majority of DNA circuits relies on freely diffusing reactants, which slows down their rate of operation substantially. Here we introduce the use of DNA-functionalized benzene-1,3,5-tricarboxamide (BTA) supramolecular polymers as dynamic scaffolds to template DNA-based molecular computing. By selectively recruiting DNA circuit components to a supramolecular BTA polymer functionalized with 10-nucleotide handle strands, the kinetics of strand displacement and strand exchange reactions were accelerated 100-fold. In addition, strand exchange reactions were also favored thermodynamically by bivalent interactions between the reaction product and the supramolecular polymer. The noncovalent assembly of the supramolecular polymers enabled straightforward optimization of the polymer composition to best suit various applications. The ability of supramolecular BTA polymers to increase the efficiency of DNA-based computing was demonstrated for three well-known and practically important DNA-computing operations: multi-input AND gates, Catalytic Hairpin Assembly and Hybridization Chain Reactions. This work thus establishes supramolecular BTA polymers as an efficient platform for DNA-based molecular operations, paving the way for the construction of autonomous bionanomolecular systems that confine and combine molecular sensing, computation, and actuation.

Covering an exceptionally wide range of bond strengths, the dynamic nature and facile tunability of dative B-N bonds is highly attractive when it comes to the assembly of supramolecular polymers and materials. This Minireview offers an overview of advances in the development of functional materials where Lewis pairs (LPs) play a key role in their assembly and critically influence their properties. Specifically, we describe the reversible assembly of linear polymers with interesting optical, electronic and catalytic properties, discrete macrocycles and molecular cages that take up diverse guest molecules and undergo structural changes triggered by external stimuli, covalent organic frameworks (COFs) with intriguing interlocked structures that can embed and separate gases such as CO2 and acetylene, and soft polymer networks that serve as recyclable, self-healing, and responsive thermosets, gels and elastomeric materials.

Phenothiazine is a heteroaromatic molecule capable of various noncovalent interactions, including halogen bonding and π-stacked association. Despite its broad use in functional materials and pharmaceutical ingredients, a systematic comparison of these interaction modes has been lacking. Here, we report a combined experimental and computational study of intermolecular interactions of phenothiazine with a prototypical halogen-bond (HaB) donor (tetrabromomethane), planar π-electron acceptors (tetracyanopyrazine and tetrafluoro-p-benzoquinone), and multifunctional species capable of both interaction types (iodo- and bromo-3,5-dinitrobenzenes). X-ray structural analysis revealed that CBr4 forms exclusively C–Br···π halogen bonds with the aromatic rings of phenothiazine, whereas all π-acceptors yield alternating donor–acceptor stacks characterized by multiple short contacts indicative of multicenter interactions. Notably, co-crystals of iodo- and bromodinitrobenzenes with phenothiazine display only π-stacked architectures. Density-functional calculations showed that isolated HaB complexes involving N, S, or π sites of phenothiazine possess comparable binding energies (≈−3 kcal mol−1), whereas π-stacked complexes are substantially stronger (≈−9–12 kcal mol−1). QTAIM, NCI, NBO, and energy-decomposition analyses indicated that while amounts of charge transfer in halogen-bonded and π-stacked complexes are comparable, the enhanced stability of the latter originates primarily from a large dispersion contribution. These results rationalize the solid-state preference for π-stacking over halogen bonding in systems where both motifs are accessible and clarify the hierarchy and physical origin of noncovalent interactions involving phenothiazine, providing guidance for the design of supramolecular assemblies and functional materials based on this versatile electron donor.

CONSPECTUS: Supramolecular complexes, including various low-molecular-mass structures and large molecular aggregates that are assembled by reversible and highly directional noncovalent interactions, have attracted more and more attention due to their fascinating and unconventional chemical and physical properties that are different from those of traditional architectures encountered by covalently linked backbones. Supramolecular complexes are by nature dynamic architectures considering the reversibility of noncovalent interactions by which small molecular monomers can assemble into specific architectures that are able to be repeatably reorganized through the assembly/disassembly processes under certain environmental factors such as temperature, concentration, and solvent conditions. The construction of supramolecular complexes by orthogonal self-assembly with different types of highly specific, noninterfering interactions is currently attracting considerable interest since they not only can dynamically self-assemble, but also can be tuned by various external stimuli through addressing each type of noncovalent interaction separately. Therefore, these dynamic supramolecular complexes, especially with external responsiveness, represent the most outstanding candidates for the future development of functional and smart materials, and even mimic the assembling process of natural systems. In this Account, we will summarize the recent advances of dynamic supramolecular complexes constructed by orthogonal self-assembly in soluiton in two sections: (1) Construction strategies for supramolecular complexes based on orthogonal self-assembly, whose dynamic behaviors with external responsiveness were not experimentally investigated but potentially existed due to the intrinsic reversibility of noncovalent bonds; (2) dynamic behaviors of multiresponsive supramolecular complexes, which were experimentally reported to exhibit reversible multi-responsiveness to external stimuli. Dynamic nature is one of intrinsic properties of supramolecular complexes constructed by self-assembly. Therefore, in the first section, we will describe the dynamic self-assembly in the construction of supramolecular complexes, but will focus on their external responsive dynamic behaviors in the second section. In addition, considering that an increasing number of supramolecular complexes constructed by biological building blocks through bio-orthogonal assembly as mimics of biological systems have been reported in recent years, in the second section we will also present some typical examples on such special dynamic biological supramolecular complexes. The final part of this Account is devoted to foreseeing the rapid development of dynamic supramolecular complexes toward applications in functional and smart materials and fundamental questions facing dynamic supramolecular complexes in the future.

Recent advances in DNA nanotechnology led to the development of biocompatible functional materials targeting different applications, including delivery, precise scaffolding, computation, etc. However, a standard toolbox of building blocks used by chemists is largely limited to canonical nucleobases. To further develop the functional potential of synthetic DNA systems, the use of sequence-specific DNA-polymer conjugates has emerged as an exciting alternative approach. Herein, we demonstrate the synthesis and self-assembly properties of monodisperse DNA-pyrene polyphosphate oligomers as essential units for DNA-grafted supramolecular polymers. Such systems become increasingly important for the creation of dynamic and stimuli-responsible materials. The unique self-recognition properties of oligonucleotides laid the foundation of modern DNA nanotechnology. Over the last two decades, man-made DNA assemblies led to the development of numerous biocompatible functional materials, including drug carriers, nanorobots, and scaffolding platforms. A standard toolbox of building blocks used by chemists in the field is largely limited to four units – A, G, C, T. To further develop the functional potential of synthetic DNA systems, the use of DNA-chromophore conjugates emerges as an exciting approach. Following our previous findings, we demonstrate herein the synthesis of the DNA-pyrene oligomers and the temperature-induced self-assembly of these conjugates into DNA-grafted supramolecular polymers. (see Figure 1). Such systems become increasingly important for the creation of dynamic and stimuli-responsible materials targeting various applications such as delivery and precise scaffolding.

On page 2572 Arri Priimagi, Pierangelo Metrangolo, Giuseppe Resnati, and co-workers report the first light-responsive halogen-bonded polymer systems and highlight the remarkable potential of halogen bonding in fundamental studies of photoresponsive azobenzene-containing polymers. Because of its directionality and tuneable interaction strength, halogen bonding is a viable tool to design high-performance supramolecular polymers for holographic inscription of surface relief gratings (SRG).

Halogen bonds in the solid state have been investigated for many years, with a major resurgence in activity occurring in the past decade. The emphasis of most studies has been on organic components. This Highlight focusses on inorganic components, or at least metal-containing components, and explores their propensity to form halogen bonds. The use of C–X⋯X′–M halogen bonds in forming networks is briefly reviewed and their utility in investigating the nature of halogen bonds is explored since their strength can be tuned by changing either the organic (donor) halogen (C–X) or the inorganic (acceptor) halogen (M–X′). A survey has been performed of crystal structures in which interactions are of suitable geometry to be considered as halogen bonds. In particular the role of simple monatomic (e.g.oxo, nitrido) and diatomic (e.g.carbonyl, cyanide) ligands as halogen bond acceptors in transition metal complexes is examined. Main group metals are also considered in a further section that considers D–X⋯A–M halogen bonds, where D = halogen bond donor, A = halogen bond acceptor and M = main group metal or metalloid. Many examples presented herein were not identified as halogen bonds in the original articles. The aim of this survey is to examine the breadth of elements that can be involved in halogen bonding involving at least one inorganic (metal-containing) component and consider this range of interactions as a basis for future research in halogen bonding with applications in crystal engineering and allied areas.

Cyclodextrins functionalized polyvinylidene fluoride membranes: Strategies and diverse applications

ConspectusRecently, supramolecular polymers (SPs), which depend on the formation of reversible bonds between monomers, have attracted attention as a class of materials that can overcome the potential environmental problems of conventional polymeric materials. The development of various supramolecular polymers is important not only for their direct application as materials but also because their unique polymerization processes and dynamic properties have a profound influence on the development of polymeric and small-molecule-based functional materials. In other words, by limiting the dimensionality of molecular assemblies to one dimension, we can discover the essential aspects of self-assembly and self-organization. In particular, supramolecular polymerization, in which π-electron-rich planar molecules are stacked one-dimensionally via multiple interactions, is interesting because it gives "π-stacked SPs" with one-dimensional crystal-like order. The excellent intrinsic (internal) structural order of π-stacked SPs is difficult to observe in higher-order structures that exhibit only a monotonous linear structure. However, our research has shown that when internal structural order intrinsically generates curvature, the curvature appears as a major feature of the entire polymer chain. This intrinsic curvature allows the formation of diverse topologies such as toroids, random coils, waves, spirals, and helicoids using π-stacked SPs and also allows structural changes at the single-polymer-chain level along a topology-dependent energy landscape. In other words, π-stacked SP-based nanomaterials could enable free control of the structure at the single-polymer-chain level. This Account will focus on our research into curved supramolecular polymers (CSPs) during the last five years. CSPs are formed by the hydrogen bonding between barbiturate-containing π-conjugated molecules to produce giant supramolecular monomers. We first give an overview of the molecular design of the monomers required for the formation of CSPs, the unique energy landscape of CSPs, and their evaluation and analysis methods, before describing the four specific properties of CSPs. The first is structural controllability via the introduction of photoresponsive units such as azobenzene and diarylethene moieties. The isomerization of these photochromic molecules within the CSP main chain has a local effect on the curvature and allows photocontrol of their entire topology. The second is the copolymerization of different molecules via the formation of rosettes. Here, two extreme examples, block and alternating copolymerization, are discussed. Third, we describe a structural transition that involves the rearrangement of hydrogen bonds. This is a new property, which enables a structural transition from a soft and highly soluble supramolecular polymer to a hard and poorly soluble crystalline structure and thus expands the applicability of CSPs to environmentally important and electronic materials. Finally, self-assembled polycatenanes are described as an example of an entirely new "topological self-organization" using CSP formation on CSP surfaces, i.e., secondary nucleation. This work is also a turning point in our CSP research and includes concepts that are broadly applicable to the creation of self-organized functional materials. At the end of this Account, we will discuss how CSPs can contribute to nanotechnology or mesotechnology as single-chain-polymer materials. We hope that the landscape depicted in this Account will guide the development of a variety of new functional materials.

The organometallic compound trans-(tetrafluoropyrid-2-yl)bis(triethylphosphine)-fluoronickel(II) (NiF) is shown to serve as a strong hydrogen bond and halogen bond acceptor in solution via intermolecular interactions with the fluoride ligand. The nature of the interactions has been confirmed by multinuclear NMR spectroscopy. Experimental binding constants, enthalpies, and entropies of interaction with hydrogen-bond-donor indole and halogen-bond-donor iodopentafluorobenzene have been determined by 19F NMR titration. In toluene-d8 solution indole forms a 1:1 and 2:1 complex with NiF (K1 = 57.9(3), K2 = 0.58(4)). Interaction enthalpies and entropies are -23.4(2) kJ mol-1 and -44.5(8) J mol-1 K-1, respectively, for the 1:1 complex; -14.8(8) kJ mol-1 and -53(3) J mol-1 K-1, respectively, for the 2:1 complex. In toluene-d8 solution iodopentafluorobenzene forms only a 1:1 complex (K1 = 3.41(9)) with enthalpy and entropy of interaction of -16(1) kJ mol-1 and -42(4) J mol-1 K-1, respectively. A marked solvent effect was observed for the halogen bond interaction. NMR titrations in heptane solution indicated formation of both 1:1 and 2:1 complexes of iodopentafluorobenzene with NiF (K1 = 21.8(2), K2 = 0.22(4)). Interaction enthalpies and entropies are -26(1) kJ mol-1 and -63(4) J mol-1 K-1, respectively, for the 1:1 complex; -21(1) kJ mol-1 and -83(5) J mol-1 K-1, respectively, for the 2:1 complex. There is a paucity of such experimental energetic data particularly for halogen bonds despite substantial structural data. These measurements demonstrate that halogen bonds are competitive with hydrogen bonds as intermolecular interactions and provide a suitable benchmark for theoretical calculations and quantitative input into design efforts in supramolecular chemistry and crystal engineering.

Functional inorganic materials are very important today to meet the needs of our society. The most demanding needs are sustainable and clean energy (it would be nice if that can be achieved from water splitting), smart materials for sensing toxic volatile as well as water-soluble substances (health care) and efficient catalysts that can cycle multiple times without deterioration for useful chemical reactions. Supramolecular chemistry, that plays a vital role to design and synthesize such functional molecules, controls over the intermolecular interactions, thereby the molecular recognition processes leading to molecular functions, e.g., sensing, catalysis, etc. This article deals with inorganic supramolecular chemistry of a number of mono-nuclear coordination complexes to selected di-nuclear systems through trinuclear metal basic carboxylates, mostly in their solid-state, leading to the functional inorganic materials. We have demonstrated that some of the very old inorganic systems can be explored in the light of supramolecular chemistry to describe them as functional materials, which have potential in serving our society to some extent. This work aims to discuss the potential applications of some of the age-old chemical systems which can be broadly classified as mononuclear complexes, dinuclear systems and trinuclear clusters. These systems can be perceived as a seedling which has the potential to grow into a tree, provided, it is supplied with all the resources and well taken care of. By the virtue of extensive research going around the world, these versatile systems have evolved through the years to grow into a field with wide-ranging applications, but still a lot remains to be explored.

This study presents a theoretical simulation of the interactions between XCN molecules (X = F, Cl, Br, and I) and phosphine amine (PA) based on ab initio calculations. Our results revealed the formation of three optimised structures, denoted as Structure-A to Structure-C. The Structures-A and C are stabilized through halogen bonding(XB) interactions of the types N···X and P···X, respectively, while structure–B corresponds to a dual, Pnictogen-Tetrel (PnB–TB) complex involving N···P and P···C interactions. The computed interaction energies established the following stability order: Structure-A > Structure-C > Structure-B. Natural Bond Orbital (NBO) analysis demonstrated that two orbital interactions, lp(N) → BD*(P–N) and lp(P) → BD*(C–N), play a critical role in stabilising the complexes of structure–B. These findings are fully consistent with the results obtained from Noncovalent Interaction (NCI) analysis, whereas the Atoms-in-Molecules (AIM) analysis did not provide satisfactory results for these systems. To achieve a deeper understanding of the properties of the resulting complexes, a series of complementary analyses were performed. These included molecular electrostatic potential (MEP), geometry optimisation, spectroscopy, interaction energy (ΔIE) calculations, Natural Bond Orbital (NBO) analysis, Atoms-in-Molecules (AIM) analysis, Noncovalent Interaction (NCI) index analysis, and Energy Decomposition Analysis (EDA).