Self-assembly multicomponent

Electrospray mass spectrometry (ESMS) is a powerful tool for gaining insight into the self-assembly process itself by allowing the identification of the species present in various solutions of such complicated mixtures of self-assembling ligands and metal ions leading up to the final architecture [9.94, 9.95]. 

Extension of the cage forming process to linear, rigid components containing three or four bipy subunits allows the generation of the triple-decker 157 or the quadruple-decker 158 cylindrical complexes with silver ions by self-assembly processes that involve a total of 15 and 19 particles [9.96], respectively. 

The factors that induce these notable self-assembly processes are both structural (ligand nature, metal ion coordination, steric) and thermodynamic (site occupancy, entropy). They will be considered in more detail below (Section 9.5). 

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Baxter, P., Lehn, J. M., Decian, A., Fischer, J., Multicomponent self-assembly - spontaneous formation of a cylindrical complex from 5 ligands and 6 metal-ions. Angew. Chem., Int. Ed. Engl. 1993, 32, 69-72. 

Sleiman, H., Baxter, P. N. W., Lehn, J. M., Airola, K., Rissanen, K., Multicomponent self-assembly Generation of rigid-rack multimetallic pseudorotaxanes. Inorg. Chem. 1997, 36, 4734-4742. 

Schmittel M, He B, Mai P (2008) Supramolecular multicomponent self-assembly of shape-adaptive nanoprisms wrapping up C60 with three porphyrin units. Org Lett 10 2513... 

Finnie, K. R. Nuzzo, R. G., The phase behavior of multicomponent self-assembled monolayers directs the nanoscale texturing of Si(100) by wet etching, Langmuir 2001, 17, 1250-1254... 

The classical thermochemical approach has also already been applied to special template-assisted chemical reactions like the template-directed synthesis of oligonucleotides [260], for which a detailed system of kinetic elementary steps has been derived and solved. Other examples are the thermochemical model for the assessment of cooperativity in self-assembly processes proposed in Ref. [261, 262] and for the quantitative description of multicomponent self-assembly processes of polymetallic helicates [263, 264]. More thermochemical approaches applied within particular fields of supramolecular chemistry will be mentioned in the following. 

Baxter. P.N.W. Hanan, G.S. Lehn, J.-M. Inorganic arrays via multicomponent self-assembly The spontaneous generation of ladder architecture. Chem. Commun. 1996. 2019-2020. 

Baxter. P.N.W. Lehn, J.-M. Kneisel, B.O. Fenske. D. Multicomponent self-assembly Preferential generation of a rectangular [2 x 3] grid by mixed ligand recognition. Angew. Chein., Int. Ed. 1997, 36. 1978-1981. 

Hamacek J, Borkovec M, Piguet C. A simple thermodynamic model for quantitatively addressing cooperativity in multicomponent self-assembly processes — part 1 theoretical concepts and application to monometallic coordination complexes and bimetallic heli-cates possessing identical binding sites. Chem Em J. 2005 1 5217—5226. 

The cobalt(II) complex is labile, and self-assembles to triple-helical [Co2(5-bismbmp)3] [24] which is readily oxidized to the cobalt(III) complex [Co2(5-bismbmp)3] which is sufficiently inert for the two enantiomers to be separated by classical methods [25]. The transformation of labile species to kinetically stable ones offers the possibility of using these elements as building blocks for further supramolecular construction. On the basis of our results with sophisticated ligand systems such as L232, we suspect that complicated, multicomponent self-assembly reactions without some element of kinetic stability will be rather difficult to develop. 

Figure 2 Synthesis of tr/s-ligand 3 and hexa/c/s-ligand 7 via Suzuki coupling and subsequent, multicomponent self-assembly into a spoked wheel 8 under thermodynamic control with Cd". Adapted with permission from Ref. iiJAi1450. Copyright 2011 American Chemical Society.

Figure 9 Multicomponent self-assembly at the liquid-graphite interface, (a) Chemical stmctures of the used molecular building blocks, (b) STM image for the mixture of the four molecules bisDBA-Ci2, COR, ISA, and TRI and (c) corresponding molecular model. The Kagome network is formed by bisDBA-Ci2 and hosts in its triangular pores single TRI molecules and in the hexagonal pores a COR-ISA6 cluster. (Reproduced from Ref. 50. Wiley-VCH, 2009.)...

Multicomponent Self-Assembled Polymers Based on JT-Conjugated Systems... 

SCHEME 4.12 Synthesis of rotaxane 20 by multicomponent self-assembly. 

N. Christinat, R. Scopelliti, K. Severin, Chem. Commun. 2008, 3660-3662. Boron-based rotaxanes by multicomponent self-assembly. 

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