Self-assembly of inorganic architectures

Numerous metallomacrocycles self-assemble from their components giving species possessing various structures, for instance triangular shape [9.30,9.31] containing a cavity [9.32], which may include a guest molecule [9.33] square [9.34,9.35] or star like [9.36-9.39] shapes wheel-shaped or toroidal hexameric [9.40], octameric [9.41] or decameric [9.42,9.43] structures square [9.44,9.45] rectangular [9.46,9.47] or bent [9.48] boxes into which substrate molecules may bind [9.49,9.50] adaman-tanoid shape [9.51,9.52] with cation inclusion [9.51c], formally related to that of the spheroidal macrotricycle 21 catenane type [9.53]. Coordination species of dendri-mer or arborol nature have been constructed [7.61, 8.27, 9.54]. 

Section 9.7). Our work involved first the self-assembly of double-helical metal complexes. This particularly interesting case of self-assembly of a coordination compound represented a first step in our studies on the design of inorganic programmed systems. 

1 Self-Assembly of Double-Helical and Triple-Helical Metal Complexes The Helicates 

Self-assembly may occur in repetitive chain ligands, acyclic coreceptors containing several identical binding subunits arranged linearly, if substrate binding to a given site is connected with binding to the other sites so that full site occupation is only compatible with a defined final architecture. 

One may draw an analogy between nucleic acids and helicates, with on one side the polynucleotide strands and their interaction through hydrogen bonding and on the other side the oligobipyridine strands and their binding together via metal ion coordination. 

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The ambidentate coordinating ability of the oxalate ion (ox = C2042 ) has made it a useful and versatile choice as a bridging ligand for the design of two- and three-dimensional compounds. Indeed, the self-assembly of inorganic architectures... 

Krische, M., Lehn, J.-M. The Utilization of Persistent H-Bonding Motifs in the Self-Assembly of Supramolecular Architectures. In Fuiita, M. (ed.) Molecular Self-Assembly Organic Versus Inorganic Approaches. Structure and Bonding, vol. 96, pp. 3-29. Springer, Berlin Heidelberg (2000). doi 10.1007/3-540-46591-X l... 

The self-assembly of these squares (Scheme ) from Re(CO)3X is highly efficient and seems thermodynamically controlled (see Self-assembled Inorganic Architectures). ... 

For all these reasons, the guanine building blocks and the sol-gel chemistry were used as molecular precursor to conceive hybrid chiral materials at nanometric and micrometric scales. Our efforts involved the synthesis and the self-assembly of a guaninesiloxane monomer Gsi (Fig. 3) in the G-quartet and G-quadruplex supramolecular architectures (Fig. 6), which are fixed in a hybrid organic-inorganic material by using a sol-gel transcription process, followed by a second inorganic transcription in silica, by calcination. 

Due to the availability of controlled polymerization routes for PFS monomers, well-defined architectures with organic and inorganic coblocks are available. The incorporation of PFS segments into self-organizing motifs, such as block copolymers, provides further possibilities for supramolecular chemistry and the development of functional nanomaterials.18-23 This section summarizes recent developments in the synthesis and self-assembly of PFS block copolymers, as well as their applications in material science. 

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