Template Synthesis (Self-Assembly) of Macrocycles: Theory and Practice
A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Molecular Structure".
Deadline for manuscript submissions: closed (30 September 2023) | Viewed by 10770
Special Issue Editor
Interests: coordination chemistry; quantum chemistry; chemistry of macrocyclic compounds; nanosciences; scientometrics
Special Issues, Collections and Topics in MDPI journals
Special Issue Information
Dear Colleagues,
More than 60 years in coordination chemistry, and since the beginning of the 21st century, and in molecular nanotechnology there is a very significant interest in template synthesis reactions, in which the design of metal complexes with complex ligands is carried out not according to the classical scheme (metal ion + ligand ® complex), but according to the scheme (metal ion + "building blocks" of the future ligand (so-called ligand synthons or ligsons) ® complex). At the same time, the preparation of such metal heterocyclic compounds by traditional methods is either difficult or even impossible. The metal ion present in the reaction system (the so-called template), which is extremely important, plays the role of a kind of pattern (template) that directs this kind of “self-assembly” in one direction or another; while in its absence it does not occur at all. In a similar way, in a number of cases, the preparation is carried out from simpler starting blocks and very complex organic compounds, which are obtained from the metal chelates formed at the beginning by means of their demetallization. The importance of this “self-assembly”, particularly that which underlies the synthesis of a number of so-called macroheterocyclic compounds, has recently shown an increasing tendency in both fundamental science and in practical terms. It should be noted that “self-assembly” reactions now occupy a dominant position in the synthesis of nitrogen-, nitrogen-oxygen-, and nitrogen-sulfur-containing macrocycles, crown ethers, and other systems with closed loops that include various heteroatoms in their framework. The end products of these reactions, having a complex with non-trivial physical and chemical properties, are due to this extremely diverse application—in addition to chemistry proper, their consumers are metallurgy and medicine, industrial biotechnology and catalysis, microelectronics and agriculture and many other branches of human activity.
Although the number of works on template synthesis currently amounts to many thousands (if not tens of thousands), in this area of chemical synthesis, the structural-chemical design and control of this synthesis, as well as the prediction of the specifics of its products, remain relevant problems. These problems clearly manifest themselves during the self-assembly of the so-called small metallocycles, the results of which in each particular case are difficult to predict, unless any close analogues of such processes are known. Sometimes even ions which are similar in geometric and electronic parameters, being in the role of a template, “organize” this self-assembly in completely different directions. Particularly interesting in the self-assembly reactions are the so-called ambidentate, primarily (N,O,S,P)-donor atomic ligand synthons, which, depending on the starting conditions of complex formation and the nature of the metal ion, are capable of being coordinated to the latter by means of various donor atoms. This circumstance opens new opportunities for the targeted synthesis of a wide variety of metal-macrocyclic compounds on the one hand, and in some cases makes it possible to obtain new, previously unknown metal complexes, which is undoubtedly valuable both for fundamental coordination and supramolecular chemistry, and for molecular nanotechnology. The foregoing is especially important at present, when the efforts of the overwhelming majority of complex chemists all over the world are directed primarily to the development of new methods for the synthesis of metal-macrocyclic and supramolecular compounds.
Considering the above, this Special Issue aims include, first of all, original full articles and brief reports on any processes for the self-assembly (template synthesis) of p-, d-, and f-element macrocyclic compounds. We also welcome papers presenting, along with experimental data, quantum chemical calculations of the molecular/electronic structures of the corresponding macrocyclic compounds, as well as papers presenting purely theoretical calculations related to compounds of this type. Review articles may also be submitted for publication in this Special Issue (including authors’ reviews focusing primarily on their own publications).
Prof. Dr. Oleg V. Mikhailov
Guest Editor
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Keywords
- macrocyclic compounds
- template synthesis
- self-assembly
- molecular structure
- thermodynamic characteristics
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