The Controlled Molecular Magnetism of Mono-, Bi- and Polynuclear Complexes Based on Hydrazones, Azomethenes and its Analogues (309,00 руб.)

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MINISTRY OF EDUCATION AND SCIENCE OF THE RUSSIAN FEDERATION Federal State Autonomous Educational Institution of Higher Education “SOUTHERN FEDERAL UNIVERSITY” V. V. Lukov I. N. Shcherbakov The controlled molecular magnetism of mono-, bi- and polynuclear complexes based on hydrazones, azomethenes and its analogues Monography Rostov-on-Don – Taganrog Publishing House of Southern Federal University 2019

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UDC 541.139(035.3) BBC 24.5я73 The monography is printed under the decision of Committee at Southern Federal university Academic council on a mathematical and natural-scientific direction of science and education (the record of proceedings № 10, April 22, 2019) Reviewers: Ph.D, Professor S.I.Levchenkov; Doctor of Sciences in Chemistry, Professor I.E.Oufljand Lukov, V. V. The controlled molecular magnetism of mono-, bi- and polynuclear complexes based on hydrazones, azomethenes and its analogues : monography / V. V. Lukov, I. N. Shcherbakov ; Southern Federal University. – Rostov-on-Don ; Taganrog : Publishing House of Southern Federal University, 2019. – 238 p. ISBN 978-5-9275-3280-3 The monography “The controlled molecular magnetism of mono-, bi-and polynuclear complexes based on hydrazones, azomethenes and its analogues” represents the encyclopedic edition reflecting the basic experimental - theoretical aspects concerning new scientific area- magnetochemistry of exchange-couple systems. Alongside with a statement of fundamental concepts of magnetism including features of isotropic and anisotropic exchange interaction, and the theory of spin transitions, the central part of the monography is devoted to the analysis of magnetochemistry’s opportunities at the description of a structure and properties of bi- and tetranuclear complexes as well as supramolecular architectures based mainly on hydrazones, azomethenes and their analogues. The interrelation between features of an electronic and geometrical structure of complexes and character of exchange effects is considered, the magneto-structural correlations in the important modelling objects for directed design of one, two and threedimensional magneto-ordered structures have been revealed. UDC 541.139(035.3) BBC 24.5я73 ISBN 978-5-9275-3280-3 © Southern Federal University, 2019 © Lukov V. V., Shcherbakov I. N., 2019

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CONTENTS Chapter I. INTRODUCTION .................................................................................... 5 Chapter II. Isotropic Interaction in Dinuclear Compounds ....................................... 8 Chapter II.1. Mechanism of Magnetic Coupling ..................................................... 11 Chapter II.2. Peculiarities of Magnetic Exchange in Binuclear Copper(II) Complexes with Organic Ligands Based on 1,3-Diaminopropan-2-ol ................... 15 List of references to Chapters I–II ........................................................................... 30 Chapter III. Magnetostructural relationships in the binuclear complexes containing heterocyclic fragments ........................................................................... 33 Chapter III.1. Complexes with the intermolecular exchange interaction translated along the system of hydrogen bonds ....................................................................... 49 Chapter III.2. Transition metal complexes containing the cubane fragment with different exchange channels .................................................................................... 62 List of references to Chapter III .............................................................................. 74 Chapter IV. Magnetochemical study of the structures of binuclear metalchelates with azomethines and hydrazones. A concept of geometrical modeling of exchange fragments ................................................................................................. 89 Chapter IV.1 Magnetochemistry of homo- and heterobinuclear complexes with 2,6-diformyl-4-R-phenol bishydrazones ............................................................... 103 Conclusion to the Chapter IV ................................................................................ 125 List of references to Chapter IV ............................................................................ 126 Chapter V. Magnetic Long-Range Ordering in Molecular Compounds: Design of Molecular-Based Magnets ..................................................................................... 141 Chapter V.1. Molecular magnetism. An interdisciplinary research field ............. 141 3

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Chapter V.1.2. Coordination chemistry approach to molecular magnetism. A suitable choice ........................................................................................................ 147 Chapter V.2. Aims and scope ................................................................................ 148 Chapter V.2.1. Molecule-based and single-molecule magnetism. Two worlds in one .......................................................................................................................... 148 Chapter V.2.2. Single-molecule magnetism. A collective voyage ........................ 151 Chapter V.3. Electron exchange and double exchange ......................................... 153 Chapter V.3.1. Homo- and heterometallic dinuclear complexes and metal-radical analogues ................................................................................................................ 153 Chapter V.3.2. Homo- and heterovalent dinuclear complexes .............................. 172 Chapter V.4. Spin crossover and valence tautomerism ......................................... 187 Chapter V.4.1.Mono- and dinuclear iron complexes and cobalt-polyoxolene radical analogues .................................................................................................... 187 Chapter V.4.2. Di- and tetranuclear iron cyanide complexes and iron-cobalt analogues ................................................................................................................ 215 Conclusion. ............................................................................................................ 225 List of references to Chapter V .............................................................................. 226 4

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