Supramolecular architecture

T. Bein, ed., Supramolecular Architecture, ACS Symposium Series, Vol. 499, American Chemical Society, Washington, DC, 1992. 

The results presented up to here concern only one-dimensional oligomers and polymers of the PPP-lype. This section is mainly focussed on the electronic properties of extended re-chains and on the morphology of solid PPPs using chain-stiffness as a structure-forming principle for supramolecular architectures. 

Electronic and Magnetic Properties of Chiral Molecules and Supramolecular Architectures... 

The reviews collected in this book convey some of the themes recurrent in nano-colloid science self-assembly, constraction of supramolecular architecture, nanoconfmement and compartmentalization, measurement and control of interfacial forces, novel synthetic materials, and computer simulation. They also reveal the interaction of a spectrum of disciplines in which physics, chemistry, biology, and materials science intersect. Not only is the vast range of industrial and technological applications depicted, but it is also shown how this new way of thinking has generated exciting developments in fundamental science. Some of the chapters also skirt the frontiers, where there are still unanswered questions. 

In this review, CPOs constructed by covalent bonds are mainly focused on however, stable coordination bonds comparable to the stability of the covalent bonds have potential for future enhanced molecular design of novel CPOs. One representative is the bond between pyridine-type nitrogen and metal, which is widely used in supramolecular chemistry, that is, the cyclic supramolecular formation reaction between pyridine-substituted porphyrin and metal salts (Fig. 6d) [27,28]. Palladium salts are frequently used as the metal salts. From the viewpoint of the hard and soft acid and base theory (HSAB), this N-Pd coordination bond is a well-balanced combination, because the bonds between nitrogen and other group X metals, N-Ni and Ni-Pt coordination bonds, are too weak and too strong to obtain the desired CPOs, respectively. For the former, the supramolecular architectures tend to dissociate into pieces in the solution state, and for the latter. 

A more complex supramolecular architecture has been discovered for the complexes [ t-N,N-pzAu]3, Figure 1.36, and [ t-N,N-4-MepzAu]3 [57]. Intramolecular... 

Eernandez, E.J., Laguna, A., Lopez-de-Luzuriaga, J.M., Monge, M Montiel, M Olmos, M.E. and Perez, J. (2004) Thallium(I) Acetylacetonate as Building Blocks of Luminescent Supramolecular Architectures. Organometallics, 23(4), 774-782. 

Harada, A, Design and Construction of Supramolecular Architectures Consisting of Cydodex-trins and Polymers. VoL 133, pp. 141-192,... 

Recent years have witnessed considerable interest in the development of rational synthetic routes to supramolecular architecture from self-assembly of component metal complexes. These solid... 

Hawthorne and co-workers have also produced a series of macrocyclic Lewis acid hosts called mercuracarborands (156, 157, and 158) (Fig. 84) with structures incorporating electron-withdrawing icosahedral carboranes and electrophilic mercury centers. They were synthesized by a kinetic halide ion template effect that afforded tetrameric cycles or cyclic trimers in the presence or absence of halide ion templates, respectively.163 These complexes, which can bind a variety of electron-rich guests, are ideal for catalytic and ion-sensing applications, as well as for the assembly of supramolecular architectures. 

Figure 88 The supramolecular architectures (171) assembled by the C—H S—H H—B hydrogen/dihydrogen-bond interactions between mercaptane and metallacarborane complexes. (Adapted from ref. 167.)...

Ajayaghosh A, Chithra P, Varghese R, Divya KP (2008) Controlled self-assembly of squaraines to ID supramolecular architectures with high molar absorptivity. Chem Com-mun 969-971... 

Many of the materials currently under development draw their inspiration from structures found in nature. That is, by mimicking the supramolecular architecture of natural materials, one can prepare complex materials capable of highly sophisticated functions. An important aspect of this work involves the selection of microorganism templates (e.g., diatomite) based on specific porous structures that may benefit targeted applications. 

The weak supramolecular interactions (H-bonds, coordination or van der Waals interactions, etc.) positioning the molecular components to give the supramolecular architectures are typically several orders of magnitude less robust than the cross-linked covalent bonds formed in a specific polymerization process. Accordingly, the sole solution to overcome these difficulties is to improve the binding (association) efficiency of the molecular components generating supramolecular assemblies. At least in theory, an increased number of interaction moieties and the selection of the... 

Design and Construction of Supramolecular Architectures Consisting of Cyclodextrins and Polymers... 

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