Supramolecular polymers exhibit fascinating structures, and their properties, and thus applications, depend both on the strength and dynamics of the non-covalent bonds and on the functional properties of the monomeric building blocks. In this Review, we highlight the progress in methods developed to control supramolecular polymerization based on physicochemical insights into the thermodynamics and kinetics of non-covalent interactions. Prerequisites for polymer formation and stability, such as high binding strength (thermodynamics) between complementary receptor units, are briefly discussed, while the main focus is on the kinetic control of pathway selectivity, which in recent years has allowed seed-induced living supramolecular polymerization, chain growth-type supramolecular polymerization and the preparation of specific supramolecular polymer polymorphs and supramolecular block copolymers. Beginning with a historical retrospective, this Review highlights the progress from thermodynamically and kinetically controlled self-assembly processes towards seed-induced living supramolecular polymerization, which allows the formation of highly ordered, functional materials such as supramolecular block copolymers.

Supramolecular polymerization through kinetic pathway control and living chain growth

Multicomponent supramolecular copolymerization promises to construct complex nanostructures with emergent properties. However, even with two monomeric components, various possible outcomes such as self-sorted supramolecular homopolymers, a random (statistical) supramolecular copolymer, an alternate supramolecular copolymer, or a complex supramolecular block copolymer can occur, determined by their intermolecular interactions and monomer exchange dynamics and hence structural prediction is extremely challenging. Herein, we target this challenge and demonstrate unprecedented two-component sequence controlled supramolecular copolymerization by manipulating thermodynamic and kinetic routes in the pathway complexity of self-assembly of the constitutive monomers. Extensive molecular dynamics simulations provided useful mechanistic insights into the monomer exchange rates and free energy of interactions between the monomers that dictate the self-assembly pathway and sequence. The fluorescent nature of core-substituted naphthalene diimide monomers has been further utilized to characterize the three sequences via Structured Illumination Microscopy (SIM).

Self-Sorted, Random, and Block Supramolecular Copolymers via Sequence Controlled, Multicomponent Self-Assembly

Since the first polymers were discovered, scientists have debated their structures. Before Hermann Staudinger published the brilliant concept of macromolecules, polymer properties were generally believed to be based on the colloidal aggregation of small particles or molecules. From 1920 onwards, polymers and macromolecules are synonymous with each other; i. e. materials made by many covalent bonds connecting monomers in 2 or 3 dimensions. Although supramolecular interactions between macromolecular chains are evidently important, e. g. in nylons, it was unheard of to proposing polymeric materials based on the interaction of small molecules. Breakthroughs in supramolecular chemistry, however, showed that polymer materials can be made by small molecules using strong directional secondary interactions; the field of supramolecular polymers emerged. In a way, we have come full circle. In this essay we give a personal story about the birth of supramolecular polymers, with special emphasis on their structures, way of formation, and the dynamic nature of their bonding. The adaptivity of supramolecular polymers has become a major asset for novel applications, e. g. in the direction for the sustainable use of polymers, but also in biomedicine and electronics as well as self-healing materials. The lessons learned in the past years include aspects that forecast a bright future for the use of supramolecular interactions in polymer materials in general and for supramolecular polymers in particular. In order to give full tribute to Staudinger in the year celebrating 100 years of macromolecules, we will show that many of the concepts of macromolecular polymers apply to supramolecular polymers, with only one important difference with fascinating consequences: the dynamic nature of the bonds that form polymer chains.

Supramolecular Polymers – we've Come Full Circle

The use of crystallization as a tool to control the self-assembly of polymeric and molecular amphiphiles in solution is attracting growing attention for the creation of non-spherical nanoparticles and more complex, hierarchical assemblies. In particular, the seeded growth method termed living crystallization-driven self-assembly (CDSA) has been established as an ambient temperature and potentially scalable platform for the preparation of low dispersity samples of core-shell fiber-like or platelet micellar nanoparticles. Significantly, this method permits predictable control of size, and access to branched and segmented structures where functionality is spatially-defined. Living CDSA operates under kinetic control and shows many analogies with living chain-growth polymerizations of molecular organic monomers that afford well-defined covalent polymers of controlled length except that it covers a much longer length scale (ca. 20 nm to 10 μm). The method has been applied to a rapidly expanding range of crystallizable polymeric amphiphiles, which includes block copolymers and charge-capped homopolymers, to form assemblies with crystalline cores and solvated coronas. Living CDSA seeded growth methods have also been transposed to a wide variety of π-stacking and hydrogen-bonding molecular species that form supramolecular polymers in processes termed "living supramolecular polymerizations". In this article we outline the main features of the living CDSA method and then survey the promising emerging applications for the resulting nanoparticles in fields such as nanomedicine, colloid stabilization, catalysis, optoelectronics, information storage, and surface functionalization.

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Emerging applications for living crystallization-driven self-assembly

Luminescence in Crystalline Organic Materials: From Molecules to Molecular Solids

Pathway complexity, hierarchical organization, out of equilibrium, and metastable or kinetically trapped species are common terms widely used in recent, high-quality publications in the field of supramolecular polymers. Often, the terminologies used to describe the different self-assembly pathways, the species involved, as well as their relationship and relative stability are not trivial. Different terms and classifications are commonly found in the literature, however, in many cases, without clear definitions or guidelines on how to use them and how to determine them experimentally. The aim of this Minireview is to classify, differentiate, and correlate the existing concepts with the help of recent literature reports to provide the reader with a general insight into thermodynamic and kinetic aspects of complex supramolecular polymerization processes. A good comprehension of these terms and concepts should contribute to the development of new complex, functional materials.

https://onlinelibrary.wiley.com/doi/pdf/10.1002/ange.201905724

Revising complex supramolecular polymerization under kinetic and thermodynamic control

/pdf/revision-komplexer-supramolekularer-polymerisation-unter-1e3aavsd3u.pdf

Revision komplexer supramolekularer Polymerisation unter kinetischer und thermodynamischer Kontrolle

In recent years, the development of sophisticated analytical tools, kinetic models and sample preparation methods has significantly advanced the field of supramolecular polymerization, where the competition of kinetic vs. thermodynamic processes has become commonplace for a wide range of building blocks. Typically, the kinetic pathways are identified in thermally controlled assembly experiments before they ultimately evolve to the thermodynamic minimum. However, there might be cases where the identification and thus the assessment of the influence of kinetic aggregates is not trivial, making the analysis of the self-assembly processes a hard task. Herein, we demonstrate that “hidden” kinetic pathways can have drastic consequences on supramolecular polymerization processes, to the point that they can even overrule thermodynamic implications. To this end, we analyzed in detail the supramolecular polymerization of a chiral PdII complex 1 that forms two competing aggregates (Agg I and Agg II) of which kinetic Agg II is formed through a “hidden” pathway, i.e. this pathway is not accessible by common thermal polymerization protocols. The hidden pathway exhibits two consecutive steps: first, Agg II is formed in a cooperative process, which subsequently evolves to clustered superstructures driven by rapid kinetics. At standard conditions, Agg II displays an extraordinary kinetic stability (>6 months), which could be correlated to its cooperative mechanism suppressing nucleation of thermodynamic Agg I. Furthermore, the fast kinetics of cluster formation sequester monomers from the equilibria in solution and prevents the system from relaxing into the thermodynamic minimum, thus highlighting the key implications of hidden pathways in governing supramolecular polymerization processes.

/pdf/consequences-of-hidden-kinetic-pathways-on-supramolecular-4wwaesbzon.pdf

Consequences of hidden kinetic pathways on supramolecular polymerization

C3‐Symmetrical π‐Scaffolds: Useful Building Blocks to Construct Helical Supramolecular Polymers

Halogens play a crucial role in numerous natural processes and synthetic materials due to their unique physicochemical properties and the diverse interactions they can engage in. In the field of supramolecular polymerization, however, halogen effects remain poorly understood, and investigations have been restricted to halogen bonding or the inclusion of polyfluorinated side groups. Recent contributions from our group have revealed that chlorine ligands greatly influence molecular packing and pathway complexity phenomena of various metal complexes. These results prompted us to explore the role of the halogen nature on supramolecular polymerization, a phenomenon that has remained unexplored to date. To address this issue, we have designed a series of archetypal bispyridyldihalogen PtII complexes bearing chlorine (1), bromine (2), or iodine (3) and systematically compared their supramolecular polymerization in nonpolar media using various experimental methods and theory. Our studies reveal a remarkably different supramolecular polymerization for the three compounds, which can undergo two competing pathways with either slipped (kinetic) or parallel (thermodynamic) molecular packing. The halogen exerts an inverse effect on the energetic levels of the two self-assembled states, resulting in a single thermodynamic pathway for 3, a transient kinetic species for 2, and a hidden thermodynamic state for 1. This seesaw-like bias of the energy landscape can be traced back to the involvement of the halogens in weak N-H···X hydrogen-bonding interactions in the kinetic pathway, whereas in the thermodynamic pathway the halogens are not engaged in the stabilizing interaction motif but rather amplify solvophobic effects.

Jonas Matern

Papers

Revising complex supramolecular polymerization under kinetic and thermodynamic control

Revision komplexer supramolekularer Polymerisation unter kinetischer und thermodynamischer Kontrolle

Consequences of hidden kinetic pathways on supramolecular polymerization

C3‐Symmetrical π‐Scaffolds: Useful Building Blocks to Construct Helical Supramolecular Polymers

Unraveling Halogen Effects in Supramolecular Polymerization