Supramolecular polymer chemistry

Supermolecules built from small molecules mainly involve intermolecular interactions. On the other hand, with macromolecules the supramolecular association may be either intermolecular, occurring between the large molecules, or intramolecular involving recognition sites located either in the main chain or in side-chain appendages, thus leading to chain folding and structuration of the macromolecular 

The directed manipulation of intermolecular interactions (hydrogen bonding, van der Waals forces, metal coordination) gives access to a supramolecular engineering of molecular assemblies and of polymers (see, for instance, [7.10-7.13, 7.44, 9.142, 9.157, 9.161-9.163]) through the design of instructed monomeric and polymeric species. It leads to the development of a supramolecular materials chemistry (see Section 9.8). 

4 Molecular Recognition-Directed Self-Assembly of Ordered Solid-State Structures 

Mixtures of the two species form associations in solution and 1 1 crystals by cocrystallization. In the crystal the components are arranged in mixed supramolec- 

the self-assembly spontaneously induces sorting of like/unlike species and generates long-range order, orientation, and left/right differentiation at the supramolecular level. Since the crystal packing consists of sheets of polar strands related to each other by translation, the entire three-dimensional structure becomes polar. 

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Ciferi A. (ed.)(2005) Supramolecular Polymers Chemistry-Scope and Perspectives, 2nd edn. CRC Taylor and Francis, Boca Raton. 

Ma, Y. Kolomchin, S. V. Zimmerman, S. C. Supramolecular polymer chemistry Self-assembling dendrimers using the DDA AAD (GC-like) hydrogen bonding motif. J. Am. Chem. Soc. 2002,124, 13757-13769. 

Lehn JM (2002) Supramolecular polymer chemistry - scope and perspectives. Polym Int 51 825-839... 

A supramolecular polymer chemistry has developed, concerning polymers of supramolecular nature generated by the self-assembly of monomers interconnected through complementary interaction/recognition groups [18-21]. 

StUl in its infancy, the field of supramolecular polymer chemistry has definitely found its own area and fixed place within the area of macromolecular and polymer chemistry. Although with a certain delay, the recognition of designed intermolecular forces as a tool to direct the ordering and function of macromolecules has now been widely acknowledged and respected. The transfer of principles of organic supramolecular chemistry is fully accomplished and used with perfection. 

Moreover, the recognition that many aspects of bulk -supramolecular polymer chemistry can be transferred to binding and recognition events on surfaces is an area still in its infancy. The binding processes of polymers, nanoparticles or other nanosized objects onto (polymeric, quasipolymeric)... 

We have described the versatile field of inclusion polymers from several directions and have tried to contribute to some broader application of cyclic host molecules for the variation of physical and chemical properties of polymers. Hopefully, this volume will be beneficial to readers of the polymer community who like to enter the fascinating field of supramolecular polymer chemistry. 

Rint P. Sijbesma (left) did his graduate research with professor Roeland Nolte at the University of Nijmegen the focus was on synthetic receptor molecules. From 1992 to 1993 he worked as a postdoctoral research assistant with professor Fred Wudl (University of California, Santa Barbara) on the synthesis of water-soluble C6o-derivatives. In 1993 he took his present position as assistant professor in the laboratories of professor E. W. Meijer, where he is working in the field of supramolecular polymer chemistry. 

Supramolecular Polymer Chemistry and Dynamic Combinatorial Polymers... 

Supramolecular polymer chemistry is thus both dynamic and combinatorial, and supramolecular polymers may be considered as DCMs. 

Laboratory of Supramolecular Polymer Chemistry, Department of Chemical Engineering and Chemistry, Institute for Complex Molecular Systems, Eindhoven University of Technology, PO Box 513, 5600 MB Eindhoven, The Netherlands e-mail r.p.sijbesma tue.nl... 

Zeng, F. Zimmerman, S.C. Kolotuchin. S.V. Reichert. D.E.C. Ma. Y. Supramolecular polymer chemistry Design. synthesis, characterization, and kinetics, thermodynamics. and fidelity of formation of self-assembled dendrimers. Tetrahedron 2002, 58. 825 - 843. 

Donor-Acceptor Interactions in Supramolecular Polymer Chemistry Strength... 

By connecting polymeric blocks via a noncovalent interaction, it is possible to obtain supramolecular diblock [80], triblock [81], or multiblock copolymers [82] (Figure 34.18). Supramolecular graft polymers are also possible [83] in fact, a very early event of supramolecular polymer chemistry that actually predated the studies of Lehn was the development of side chain-functionahzed polymers by Kato and Frechet [84]. In most cases, hydrogen-bonding arrays are used, due to their strength and directionality. 

Harada, A., Supramolecular Polymer Chemistry. Wiley-VCH Weinheim, 2012. 

Eindhoven University of Technology Chemical Engineering and Chemistry Supramolecular Polymer Chemistry PO Box 513, Helix STO 4.43 5600 MB Eindhoven The Netherlands... 

An overview on supramolecular polymer chemistry is presented in combination with a discussion of several potential smart systems based on hydrogen bonding and metal-ligand interactions. For a particular system, terpyridine-metal, the switchable properties are discussed in [291]. 

Supramolecular polymer chemistry, as introduced by Jean-Marie Lehn, is a relatively new field which has emerged... 

Stadler and coworkers have made important contributions to the field of supramolecular polymer chemistry through their studies of polybutadienes derivatized with hydrogenbonding phenylurazole derivatives (Figure 2). Lightscattering experiments, optical measurements, and thermal analysis were used to probe the formation of thermoplastic elastomers and elastomeric blends at lower temperatures, hydrogen bonding contributes to network formation and elastic behavior, whereas at higher temperatures these... 

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