Fascination with supramolecular chemistry over the last few decades has led to the synthesis of an ever-increasing number of elegant and intricate functional structures with sizes that approach nanoscopic dimensions Today, it has grown into a mature field of modern science whose interfaces with many disciplines have provided invaluable opportunities for crossing boundaries both inside and between the fields of chemistry, physics, and biology This chemistry is of continuing interest for synthetic chemists; partly because of the fascinating physical and chemical properties and the complex and varied aesthetically pleasing structures that supramolecules possess For scientists seeking to design novel molecular materials exhibiting unusual sensing, magnetic, optical, and catalytic properties, and for researchers investigating the structure and function of biomolecules, supramolecular chemistry provides limitless possibilities Thus, it transcends the traditional divisional boundaries of science and represents a highly interdisciplinary field

In the early 1960s, the discovery of ‘crown ethers’, ‘cryptands’ and ‘spherands’ by Pedersen,1 Lehn,2 and Cram3 respectively, led to the realization that small, complementary molecules can be made to recognize each other through non-covalent interactions such as hydrogen-bonding, charge-charge, donor-acceptor, π-π, van der Waals, etc Such ‘programmed’ molecules can thus be self-assembled by utilizing these interactions in a definite algorithm to form large supramolecules that have different physicochemical properties than those of the precursor building blocks Typical systems are designed such that the self-assembly process is kinetically reversible; the individual building blocks gradually funnel towards an ensemble that represents the thermodynamic minimum of the system via numerous association and dissociation steps By tuning various reaction parameters, the reaction equilibrium can be shifted towards the desired product As such, self-assembly has a distinct advantage over traditional, stepwise synthetic approaches when accessing large molecules

It is well known that nature has the ability to assemble relatively simple molecular precursors into extremely complex biomolecules, which are vital for life processes Nature’s building blocks possess specific functionalities in configurations that allow them to interact with one another in a deliberate manner Protein folding, nucleic acid assembly and tertiary structure, phospholipid membranes, ribosomes, microtubules, etc are but a selective, representative example of self-assembly in nature that is of critical importance for living organisms Nature makes use of a variety of weak, non-covalent interactions such as hydrogen–bonding, charge–charge, donor–acceptor, π-π, van der Waals, hydrophilic and hydrophobic, etc interactions to achieve these highly complex and often symmetrical architectures In fact, the existence of life is heavily dependent on these phenomena The aforementioned structures provide inspiration for chemists seeking to exploit the ‘weak interactions’ described above to make scaffolds rivaling the complexity of natural systems

The breadth of supramolecular chemistry has progressively increased with the synthesis of numerous unique supramolecules each year Based on the interactions used in the assembly process, supramolecular chemistry can be broadly classified in to three main branches: i) those that utilize H-bonding motifs in the supramolecular architectures, ii) processes that primarily use other non-covalent interactions such as ion-ion, ion-dipole, π–π stacking, cation-π, van der Waals and hydrophobic interactions, and iii) those that employ strong and directional metal-ligand bonds for the assembly process However, as the scale and degree of complexity of desired molecules increases, the assembly of small molecular units into large, discrete supramolecules becomes an increasingly daunting task This has been due in large part to the inability to completely control the directionality of the weak forces employed in the first two classifications above Coordination-driven self-assembly, which defines the third approach, affords a greater control over the rational design of 2D and 3D architectures by capitalizing on the predictable nature of the metal-ligand coordination sphere and ligand lability to encode directionality Thus, this third strategy represents an alternative route to better execute the “bottom-up” synthetic strategy for designing molecules of desired dimensions, ranging from a few cubic angstroms to over a cubic nanometer For instance, a wide array of 2D systems: rhomboids, squares, rectangles, triangles, etc, and 3D systems: trigonal pyramids, trigonal prisms, cubes, cuboctahedra, double squares, adamantanoids, dodecahedra and a variety of other cages have been reported As in nature, inherent preferences for particular geometries and binding motifs are ‘encoded’ in certain molecules depending on the metals and functional groups present; these moieties help to control the way in which the building blocks assemble into well-defined, discrete supramolecules4

Since the early pioneering work by Lehn5 and Sauvage6 on the feasibility and usefulness of coordination-driven self-assembly in the formation of infinite helicates, grids, ladders, racks, knots, rings, catenanes, rotaxanes and related species,7 several groups - Stang,8 Raymond,9 Fujita,10 Mirkin,11 Cotton12 and others13,14 have independently developed and exploited novel coordination-based paradigms for the self-assembly of discrete metallacycles and metallacages with well-defined shapes and sizes In the last decade, the concepts and perspectives of coordination-driven self-assembly have been delineated and summarized in several insightful reviews covering various aspects of coordinationdriven self-assembly15 In the last decade, the use of this synthetic strategy has led to metallacages dubbed as “molecular flasks” by Fujita,16 and Raymond and Bergman,17 which due to their ability to encapsulate guest molecules, allowed for the observation of unique chemical phenomena and unusual reactions which cannot be achieved in the conventional gas, liquid or solid phases Furthermore, these assemblies found applications in supramolecular catalysis18,19 and as nanomaterials as developed by Hupp20 and others21,22

This review focuses on the journey of early coordination-driven self-assembly paradigms to more complex and discrete 2D and 3D supramolecular ensembles over the last decade We begin with a discussion of various approaches that have been developed by different groups to assemble finite supramolecular architectures The subsequent sections contain detailed discussions on the synthesis of discrete 2D and 3D systems, their functionalizations and applications

Supramolecular coordination: self-assembly of finite two- and three-dimensional ensembles.

The Golden Age of Transfer Hydrogenation

An overview of the wide range of nanoreactors that have been constructed from synthetic and biological building blocks using both covalent and noncovalent approaches is given. Focus is on self-assembled systems, varying in size from a few nanometers to tens of micrometers. The review is divided into several sections that cover the development of tailor-made nanoreactors, starting from small organic molecular containers expanding to large compartment-containing assemblies. First, the construction of capsules from low molecular weight compounds by means of covalent synthesis and self-assembly by highly directive and pre-designed interactions is discussed. Second, nanocapsules based on micellar and vesicular assemblies that are built up frow low molecular weight molecules are described. Finally, the construction of nanoreactors from macromolecular building blocks, as well as recent developments in the use of viruses as nanocontainers and reactors are outlined.

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Self-Assembled Nanoreactors

Over the past decade, solvent resistant nanofiltration (SRNF) has gained a lot of attention, as it is a promising energy- and waste-efficient unit process to separate mixtures down to a molecular level This critical review focuses on all aspects related to this new burgeoning technology, occasionally also including literature obtained on aqueous applications or related membrane processes, if of relevance to understand SRNF better An overview of the different membrane materials and the methods to turn them into suitable SRNF-membranes will be given first The membrane transport mechanism and its modelling will receive attention in order to understand the process and the reported membrane performances better Finally, all SRNF-applications reported so far – in food chemistry, petrochemistry, catalysis, pharmaceutical manufacturing – will be reviewed exhaustively (324 references)

Solvent resistant nanofiltration: separating on a molecular level

In this article we describe the synthesis, characterization, and applications of dendrimer-encapsulated nanoparticles (DENs). These materials are synthesized by a template approach in which metal ions are extracted into the interior of dendrimers and then subsequently chemically reduced to yield nearly size-monodisperse particles having dimensions of less than 3 nm. Monometallic, bimetallic (including core/shell), and semiconductor nanoparticles have been prepared by this route. The dendrimer component of these composites serves not only as a template for preparing the nanoparticle replica but also to stabilize the nanoparticle, makes it possible to tune solubility, and provides a means for immobilization of the nanoparticle on solid supports. These materials have a number of potential applications, but the focus here is on catalysis. Homogeneous catalytic reactions, including hydrogenations, Heck coupling, and Suzuki reactions, in water, organic solvents, biphasic fluorous/organic solvents, and liquid an...

Synthesis, characterization, and applications of dendrimer-encapsulated nanoparticles.

Dendrimers as support for recoverable catalysts and reagents.

Dendritic phosphoramidite ligands in Rh-catalysed asymmetric hydrogenations

Divergent synthesis of carbosilane wedges as dendritic building blocks: a new strategy towards core functionalised carbosilane dendrimers

Dendrimers as Support for Recoverable Catalysts and Reagents

A divergent route for the synthesis of carbosilane wedges that contain either a bromine or amine as focal point has been developed. These new building blocks enable the construction of various core-functionalized carbosilane dendrimers. As a typical example carbosilane dendrimers up to the third generation containing a N,N′,N″-1,3,5-benzenetricarboxamide core (G1–G3) have been synthesized. This new class of molecules has been studied as host molecules and they have been found to bind protected amino acids as guest molecules via hydrogen bonding interactions. A decrease in the association constants was observed for the higher generation dendritic hosts, which is attributed to the increased steric hindrance around the core where the binding site is located. The binding properties of the dendritic host molecules can be tuned by modifying the binding motif at the core of the carbosilane dendrimers. A higher association constant for N-CBZ-protected glutamic acid 1-methyl ester (5) was observed when the third generation N,N′,N″-1,3,5-tris(L-alaninyl)benzenetricarboxamide core-functionalized carbosilane dendrimer (G3′) was used as the host molecule compared to G3. Different association constants for the formation of the diastereomeric G3′·L-5 (K = 295 M−1) and G3′·D-5 (K = 236 M−1) host–guest complexes were observed, pointing to a small enantioselective recognition effect. The difference between the association constants for the formation of the G3′·(L-5)2 and G3′·(D-5)2 host–guest complexes was much more pronounced, K = 37 M−1versusK = 10 M−1, respectively.

Rieko van Heerbeek

Papers

Dendrimers as support for recoverable catalysts and reagents.

Dendritic phosphoramidite ligands in Rh-catalysed asymmetric hydrogenations

Divergent synthesis of carbosilane wedges as dendritic building blocks: a new strategy towards core functionalised carbosilane dendrimers

Dendrimers as Support for Recoverable Catalysts and Reagents

Synthesis of carbosilane dendritic wedges and their use for the construction of dendritic receptors