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Coordination polymersCoordination polymer is the term given in inorganic chemistry to a metal coordination compound where a ligand bridges between metal centres, where each metal centre binds to more than one ligand to create an infinite array of metal centres e.g a polymer. The majority of common halides and oxides are coordination polymers. More conventionally, the term coordination polymer is reserved for compounds where the metals are bridged by polyatomic ligands, such as cyanide, carboxylates. One of the first coordination compounds ever studied systematically, Prussian blue, is a coordination polymer based on Fe-CN-Fe linkages. Additional recommended knowledge
CarboxylatesExamples of such materials include many of the metal salts of benzene-1,3,5-tricarboxylic acid (trimesic acid, BTC). This tricarboxylic acid has been one of the most popular bridging ligands used in the synthesis of these polymers. The first major paper on the topic of coordination polymers using BTC was by Yaghi et al. [1]. The senior author on this paper was O. M. Yaghi who has since published a large amount on coordination polymers. A series of solid polymers have been made via the reaction of this tri-acid with salts of cobalt, manganese, zinc, cadmium, copper, lead, uranium and other metals. Other di- and tricarboxylic acids have been used to form polymers [2] One rare but important pair of acids are 4,6-dinitro-5-hydroxyisophthalic acid and 2,4-dinitro-3-hydroxybenzoic acid which are formed by the reaction of a mixture of lead(II) nitrate, nickel nitrate, pyridine and 5-hydroxyisophthalic acid inside an autoclave. The resulting acids then form mixed lead/nickel polymers [3] It is the case that by using a non bridging ligand such as 2,2'-bipyridine on a first row transition metal (such as zinc, manganese or cobalt) a less cross linked polymer can be obtained than that which is formed by the reaction of BTC and the simple metal salt in the absence of the non bridging ligand. [4] A common type of solid formed using BTC is a layered solid where the benzene rings are coplanar with the planes. This is a layered solid which is similar to graphite in the fact that it is colvently bonded layers which are arranged on top of each other [5] PolypyridinesAnother common synthetic method is to react a polypyridine whose geometry renders it unable to chelate a metal atoms with all its nitrogen atoms. For instance 4,4'-bipyridine can be used to form polymers with many metals. One of the most developed metals is cadmium, it is the case that cadmium nitrate reacts with a wide array of polypyridines to form different solids. One of the key developments is the use of exotic polypyridines where the pyridine rings are separated by covalent spacers such as prop-1,3-diyl groups.[6] Bridging at a single atomYet another method of forming coordination polymers is to use a donor atom which bears more than one lone pair for instance this type of bridging has been seen in uranium fluorides and the lead carboxylates.
References
Illustrative discoveries
Reviews of coordination polymers
See alsoCategories: Organometallic chemistry | Coordination chemistry | Chemical reactions | Polymer chemistry |
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This article is licensed under the GNU Free Documentation License. It uses material from the Wikipedia article "Coordination_polymers". A list of authors is available in Wikipedia. |