Supramolecular classes

A second class of monolayers based on van der Waal s interactions within the monolayer and chemisorption (in contrast with physisorption in the case of LB films) on a soHd substrate are self-assembled monolayers (SAMs). SAMs are well-ordered layers, one molecule thick, that form spontaneously by the reaction of molecules, typically substituted-alkyl chains, with the surface of soHd materials (193—195). A wide variety of SAM-based supramolecular stmctures have been generated and used as functional components of materials systems in a wide range of technological appHcations ranging from nanoHthography (196,197) to chemical sensing (198—201). 

Cyclophanes or 7r-spherands have played a central role in the development of supramolecular chemistry forming an important class of organic host molecules for the inclusion of metal ions or organic molecules via n-n interactions. Particular examples are provided by their applications in synthesis [80], in the development of molecular sensors [81], and the development of cavities adequate for molecular reactions with possible applications in catalysis [82]. The classical organic synthesis of cyclophanes can be quite complex [83], so that the preparation of structurally related molecules via coordination or organometallic chemistry might be an interesting alternative. 

The use of ordered supramolecular assemblies, such as micelles, monolayers, vesicles, inverted micelles, and lyotropic liquid crystalline systems, allows for the controlled nucleation of inorganic materials on molecular templates with well-defined structure and surface chemistry. Poly(propyleneimine) dendrimers modified with long aliphatic chains are a new class of amphiphiles which display a variety of aggregation states due to their conformational flexibility [38]. In the presence of octadecylamine, poly(propyleneimine) dendrimers modified with long alkyl chains self-assemble to form remarkably rigid and well-defined aggregates. When the aggregate dispersion was injected into a supersaturated... 

Square-planar zinc compounds predominate with these ligand types as would be predicted. This is in contrast to the prevalence of tetrahedral or distorted tetrahedral geometries for four-coordinate species that have been discussed thus far. Zinc porphyrin complexes are frequently used as building blocks in the formation of supramolecular structures. Zinc porphyrins can also act as electron donors and antenna in the formation of photoexcited states. Although the coordination of zinc to the porphyrin shows little variation, the properties of the zinc-coordinated compounds are extremely important and form the most extensively structurally characterized multidentate ligand class in the CSD. The examples presented here reflect only a fraction of these compounds but have been selected as recent and representative examples. Expanded ring porphyrins have also... 

Another important class of pigment are the so-called toner pigments. These are water-soluble dyes containing sulfonic acid groups which are insolubilized by forming a salt with a divalent cation such as calcium and barium5 (Scheme 2). Until recently the toner pigments were perceived merely as insoluble salts but X-ray studies have shown them to exist as supramolecular metal complexes (see Section 9.12.4.2). 

Supramolecular Aspects of Structures from Classes of Compounds discussed in Previous Chapters 834... 

In the field of porous supramolecular metal complexes, both molecular and extended-solid materials have been extensively studied in recent years. A particularly well-studied class of compounds is the metal-containing molecular squares, that is, square-shaped porous tetrameric structures (30,108). These have been prepared by several approaches, the most common being the reaction of an organic bridging ligand with a metal complex that has available cis-coordination sites (109-113) (Fig. 13). However, the resulting metal centers are usually coordinatively saturated, which makes it difficult for guest molecules to interact directly with the metal atoms. 

In accord with general Eyring TS theory, we may consider every elementary chemical reaction to be associated with a unique A- B supramolecular complex that dictates the reaction rate. In the present section we examine representative TS complexes from two well-known classes of chemical reactions Sn2 nucleophilic displacement reactions... 

Supramolecular architectures in which transition metal cationic centres are linked via hydrogen-bonded supramolecular synthons [1,2] comprise an increasingly important class of inorganic co-ordination polymers [3], owing to their multi-dimensional, multi-functional network structures. 

Class 3 fluorophores linked, via a spacer or not, to a receptor. The design of such sensors, which are based on molecule or ion recognition by a receptor, requires special care in order to fulfil the criteria of affinity and selectivity. These aspects are relevant to the field of supramolecular chemistry. The changes in photophysical properties of the fluorophore upon interaction with the bound analyte are due to the perturbation by the latter of photoinduced processes such as electron transfer, charge transfer, energy transfer, excimer or exciplex formation or disappearance, etc. These aspects are relevant to the field of photophysics. In the case of ion recognition, the receptor is called an ionophore, and the whole molecular sensor is... 

Two types of micellar systems have been described, the first one includes Gd complexes capable of self-organization resulting in a supramolecular assembly 103), while the other class of micelles, also named mixed micelles is made of several components a lipophilic gadolinium chelate, one or several phospholipid(s) and a non-ionic surfactant containing a polyoxyethylene chain 104,105). 

Recently, a new class of supramolecular CpRu-containing catalysts for hydration of alkynes has emerged. These catalysts are based on the supramolecular self-assembly of monodentate ligands through hydrogen bonding association, as shown in Scheme 10.9 [41-43]. The remarkable activity of catalytic systems such as 15-17... 

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