Supramolecular template synthesis

M. S. Wong, H. C. Huang, and J. Y. Ying, Supramolecular-templated synthesis of nanoporous zirconia-silica catalysts, Chem. Mater. 14(5), 1961—1973 (2002). 

In this review, we tried to cover all the supramolecular species that maybe classified as rotaxane dendrimers. We classified them by their structures - where in dendrimer rotaxane-hke features are introduced. Several different types of macrocycles have been employed as a ring component in the templated synthesis of rotaxane dendrimers. While the synthesis of Type I and II rotaxanes dendrimers is relatively straightforward, that of well-defined Type III rotaxane dendrimers, particularly those of second and higher generations, is still challenging. 

Template Synthesis of Mesoporous Solids with Supramolecular Assemblies... 

Eurlan RLE, Otto S, Sanders JKM. Supramolecular templating in thermodynamically controlled synthesis. Ptoc Natl Acad Sci USA 2002 99 4801-4804. 

Figure 51. Anionic template synthesis of rotaxane 118 with a bis(phenyl ether) axle. The mechanical bond is formed by reaction of the phenolate-macrocycle complex [32-115] (supramolecular nucleophile) with the semiaxle intermediate 117. 

Since the first synthesis of mesoporous M41S alumosilicates in 1992 [1,2] numerous systems of mesoporous materials have been reported. The principle method of these syntheses consists of the utilisation of lyotropic liquid crystals as supramolecular templates, which act as structure directing agents in order to mesostructure inorganic building units. 

Ying, J. Y, Mehnert, C. P, and Wong, M. S., Synthesis and applications of supramolecular-templated mesoporous materials. Angew. Chem. Int Ed. 38,56 (1999). 

The synthesis of molecular sieves with large pores is of great importance for many applications such as catalysis, separation, adsorption and fabrication of various quantum materials [1-7]. With the recent discovery of hexagonal and cubic large pore mesoporous materials (SBA-15, SBA-16, FDU-1) [2,3], block copolymers have turned out to be valuable supramolecular templates for the synthesis of ordered large pore mesoporous materials because of their facile structure-directing ability, low-cost commercial availability and biodegradability. 

J.Y. Ying, C.P. Mehnert, M.S. Wong, Synthesis and Applications of Supramolecular-Templated Mesoporous Materials , Angew. Chem. Int. Ed., 38,56 (1999)... 

At present, the known catenanes can be divided into two categories - those prepared by metal template synthesis and those synthesised in the absence of a metalion influence. A considerable number of catenanes of the first type have been prepared by Sauvage et al. as well as by a number of other workers. However, discussion on these important metal-ion-directed systems is deferred to the next chapter in which particular supramolecular assemblies produced by metal-ion-controlled procedures are discussed. 

Ying JY, Mehnert CP, Wong MS (1999) Synthesis and appheations of supramolecular-templated mesoporous materials. Angew Chem Int Ed 38 56... 

Block copolymers are valuable supramolecular templates for the synthesis of ordered large-pore mesoporous silica and other metal oxides because of their simple templating ability, low-cost commercial availability, and biodegradability. 

Uchida, M., Kang, S., Reichhardt, C., Harlen, K., Douglas, T. (2010). The ferritin superfamily supramolecular templates for materials synthesis. Biochimica et Biophysica Acta, 1800, 834—845. 

Templated synthesis is a timely research area where molecular and supramolecular sciences meet. Moreover, it represents an emerging interface between chemistry, biology, and materials sciences. This multi-author monograph includes authoritative contributions from ten leading research laboratories involved in the development of novel template-assisted organic synthesis at this interface. It demonstrates how non-covalent and covalent templates are successfully applied to control the rate and the regio- and stereoselectivity of molecular and supramolecular organic reactions. 

---