Molecular complexity aluminosilicate

The structural complexity of the 3D framework aluminosilicates precludes a detailed treatment here, but many of the minerals are of paramount importance. The group includes the feldspars (which are the most abundant of all minerals, and comprise 60% of the earth s crust), the zeolites (which find major applications as molecular sieves, desiccants, ion exchangers and water softeners), and the ultramarines which, as their name implies, often have an intense blue colour. All are constructed from Si04 units in which each O atom is shared by 2 tetrahedra (as in the various forms of Si02 itself), but up to one-half of the Si... 

In addition to stabilizing organic products by reaction with metal-exchanged clays, as indicated above, aluminosilicate minerals may enable the preparation of metal organic complexes that cannot be formed in solution. Thus a complex of Cu(II) with rubeanic acid (dithiooxamide) could be prepared by soaking Cu montmorillonite in an acetone solution of rubeanic acid (93). The intercalated complex was monomeric, aligned with Its molecular plane parallel to the interlamellar surfaces, and had a metal ligand ratio of 1 2 despite the tetradentate nature of the rubeanic acid. 

In addition, several quantum chemical calculations of hydrated clay minerals with organic molecules using small cluster models of minerals, which consist of only several Al, Si, O, and H atoms, were published. Using small molecular models, aqueous aluminum acetate complexes [100, 101] and hydrolysis of a three-membered aluminosilicate ring were studied [102], Using... 

Microporous materials with regular pore architectures comprise wonderfully complex structures and compositions. Their fascinating properties, such as ion-exchange, separation, and catalysis, and their roles as hosts in nanocomposite materials, are essentially determined by their unique structural characters, such as the size of the pore window, the accessible void space, the dimensionality of the channel system, and the numbers and sites of cations, etc. Traditionally, the term zeolite refers to a crystalline aluminosilicate or silica polymorph based on comer-sharing TO4 (T = Si and Al) tetrahedra forming a three-dimensional four-connected framework with uniformly sized pores of molecular dimensions. Nowadays, a diverse range of zeolite-related microporous materials with novel open-framework stmctures have been discovered. The framework atoms of microporous materials have expanded to cover most of the elements in the periodic table. For the structural chemistry aspect of our discussions, the second key component of the book, we have a chapter (Chapter 2) to introduce the structural characteristics of zeolites and related microporous materials. 

Zeolites are a subclass of microporous materials in which the crystalline inorganic framework is composed of four-coordinated species interconnected by two-coordinated species. Traditionally these materials are aluminosilicates however, many different compositions have been synthesized. The templates used in the synthesis of microporous materials are typically small ionic or neutral molecular species. The function of the template in the synthesis of microporous materials is little understood, and there are at least four different modes by which an additive can operate in a zeolite synthesis a) It may act as a space filler occupying the voids in the structure, thereby energetically stabilizing less dense inorganic framework b) the additive may control the equilibria in the synthesis mixture, such as solution pH or complexation equilibria c) it may preorganize the solution species to favor the nucleation of a specific structure d) it may act as a true template determining the size and the shape of the voids in the structure. 

The crystal structure of zeolites is a complex arrangement of aluminosilicate tetrahedra, characterized by the presence of peculiar channels and cavities. Computer aided molecular graphics can represent an... 

---