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Clathrochelates are compounds which contain a metal ion encapsulated within a three dimensional cage of macrobicyclic ligand atoms. Within this cage the metal has unique properties and is to a great extent isolated from environmental factors. Such complexes are suitable as models of the most essential biological systems, membrane transport, electron carriers, highly selective and sensitive analytical reagents, catalysts for photochemical and redox processes, cation and anion receptors, etc. The aim of this monograph is to generalize and analyze experimental and theoretical data on clathrochelates in order to promote further research in this promising field of chemistry.Chapter 1 gives general concepts of complexes with encapsulated metal ions, discusses basic specific features of these compounds, considers and characterizes the main types of compounds with encapsulated metal ions and the main classes of clathrochelates, and includes the current nomenclature. Chapter 2 deals with the pathways of clathrochelate synthesis and the general procedures for the synthesis of macrobicyclic tris-dioximates, phosphorus-containing tris-diiminates, sepulchrates, sarcophagi-nates, and polyene and other types of clathrochelate complexes. Chapter 3 concerns studies of the electronic and spatial structure of clathrochelate complexes. In Chapter 4, the kinetics and mechanism of synthesis and decomposition reactions of macrobicyclic tris-dioximates, sarcophaginates, and sepulchrates in solution and gas phases are discussed. Chapter 5 considers the electrochemical, photochemical, and some other characteristics of clathrochelates and their applications associated with these characteristics. Finally, the practical applications of the unique properties of clathrochelates and perspectives on the synthesis of new clathrochelates are described in Chapters 6 and 7, respectively.
At the beginning of this book, and in the absence of guidance from IUPAC, it is appropriate to clarify the term 'chemical sensor'. A chemical sensor may be defined as a simple-to-use, robust device that is capable of reliable quantitative or qualitative recognition of atomic, molecular or ionic species. It is hard to imagine a field of applied chemistry in which a significant impact could not be made by such a device. Undoubtedly, it is this potential that has fuelled the contemporary preoccupation with chemical sensors. An unfortunate side-effect of this otherwise welcome interest is the use of the term 'chemical sensor' to add the chemical equivalent of a 'High-Tech gloss' to a rather ordinary device, publication, conference or research group. This loose usage of terminology is responsible in part for the ambiguity that surrounds many chemists' concepts of the form and function of chemical sensors. Further ambiguity arises from the extravagant claims that have been made for some sensors, and the impression that has been given of much 'verging-on-a-breakthrough' research. The research chemist engaged in sensor development should be mindful of the fact that the ultimate target for these devices is the real world, and that a successful laboratory device operating under well-defined conditions and careful calibration does not constitute a chemical sensor. Research into chemical sensors is not a recent phenomenon; it has been under way for over 80 years.