Coordination polymers chemical synthesis

Hybrid framework compounds, including both metal-organic coordination polymers and systems that contain extended inorganic connectivity (extended inorganic hybrids), have recently developed into an important new class of solid-state materials. We examine the diversity of this complex class of materials, propose a simple but systematic classification, and explore the chemical and geometrical factors that influence their formation. We also discuss the growing evidence that many hybrid frameworks tend to form under thermodynamic rather than kinetic control when the synthesis is carried out under hydrothermal conditions. Finally, we explore the potential applications of hybrid frameworks in areas such as gas separations and storage,... 

These principles of crystal engineering and supramolecular synthesis have thus far been used to design, isolate, and characterize network structures from relatively small molecular components. In the context of coordination polymer networks, a recent review indicates how wide the range of chemical components and accessible network motifs has become.48b However, the scale of these structures is such that cavities and channels are on the order of 1 nm and, to date, each cavity is identical. Careful selection of appropriate substrates or components and ever more control over crystal packing will offer the potential for rational design of an even more extensive array of modular (i.e. binary, ternary, or even higher order) structures than those that are currently available. In particular, judicious choice of supermolecules... 

Ma, B., Gao, S., Jin, T, Wang, Z., Yi, T, Liao, C. et al. (1999) One-dimensional coordination polymer [Tm2(ttha)(H20)6Tm2(ttha)(H20)4]-21H20 n synthesis, crystal structure, thermal behavior and magnetism (Hettha = triethylenetetraminehexaacetic acid). Journal of Chemical Research, Synopses, 464-465, 1938-1951. 

The synthesis and characterization of coordination polymers was supported by the U.S. Air Force in a search for materials that exhibited high thermal stabilities. However, attempts to prepare stable, tractable coordination polymers that simulate the exceptional thermal and/or chemical stability of model monomeric coordination compounds such as copper(II) ethylenediaminobisacetylacetonate or phthalocyanine have been disappointing ". Typically, only short chains are formed, and the thermally stable monomers lose most of their stability when linked by the metals into polymeric units. The principles in designing coordination polymers are ... 

D compounds could also be of interest for the design of optical devices. Indeed, in coordination polymers, inter-lanthanide distances can be controlled. This allows the synthesis of compounds with a high content in lanthanide ions. Furthermore the chemical likeness of the lanthanide ions allows the synthesis of hetero di-lanthanide compounds with a veiy good random distribution of the two rare earths. This property could be used for diluting the optically active lanthanide in a given ftamewoik or for enhancing optical properties thanks to up-conversion phenomena for instance. 

Here, the concept was put forward that once formed, in situ synthetic modification of three-dimensional coordination polymers is possible, a process now realized and termed postsynthetic modification Motivations are obvious in that naturally distinct chemical and physical properties will ensue but also that this methodology allows the introduction of functional groups that may not survive normal methods of synthesis. Often, postsynthetic modification encompasses the reaction of an incorporated subsfiate with an introduced reagent. " Introducing new chemical... 

The structural and chemical diversity of compounds containing the Si-N-P linkage is a result of both the variety of coordination numbers which phosphorus may assume and the reactivity of the Si-N bond. The combination of these features gives Si-N-P compounds very promising synthetic utility, particularly in the area of inorganic polymer synthesis. 

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