Single-Molecule Magnets (SMMs) are discrete molecules that exhibit slow relaxation of magnetization. Unlike conventional magnets that rely on the long range magnetic ordering in the form of domains, these molecules act as magnets independently, that is without the influence of neighbouring molecules. SMMs have intrigued physicists and chemists alike for over twenty years with their potential future applications in data storage quantum computing, and with this communal interest there has been significant collaboration between the two fields of research. SMMs have brought forth an opportunity for coordination chemists to muster their creativity and synthetic expertise in the rational design and development of these magnetic materials. From these new and fascinating compounds, both experimental and theoretical physicists have sought to develop and refine our understanding of the aspects of these molecular magnets in order to improve their performance at higher temperatures. In this work, new topologies for lanthanide complexes are explored using a novel Schiff base ligand. The magnetic properties of dinuclear, tetranuclear and octanuclear lanthanide complexes are discussed and correlated to their structural properties. The rational design of tetrazine-based Schiff base ligands for magnetic studies is also discussed in hopes of developing high performance SMMs.

This book begins by providing basic information on single-molecule magnets (SMMs), covering the magnetism of lanthanide, the characterization and relaxation dynamics of SMMs and advanced means of studying lanthanide SMMs. It then systematically introduces lanthanide SMMs ranging from mononuclear and dinuclear to polynuclear complexes, classifying them and highlighting those SMMs with high barrier and blocking temperatures – an approach that provides some very valuable indicators for the structural features needed to optimize the contribution of an Ising type spin to a molecular magnet. The final chapter presents some of the newest developments in the lanthanide SMM field, such as the design of multifunctional and stimuli-responsive magnetic materials as well as the anchoring and organization of the SMMs on surfaces. In addition, the crystal structure and magnetic data are clearly presented with a wealth of illustrations in each chapter, helping newcomers and experts alike to better grasp ongoing trends and explore new directions. Jinkui Tang is a professor at Changchun Institute of Applied Chemistry, Chinese Academy of Sciences. Peng Zhang is currently pursuing his PhD at Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, with a specific focus on the molecular magnetism of lanthanide compounds under the supervision of Prof. Jinkui Tang.

This thesis will present the synthesis, characterization and magnetic measurements of lanthanide complexes with varying nuclearities (Ln, Ln2, Ln3 and Ln4). EuIII, GdIII, TbIII, DyIII, HoIII and YbIII have been selected as the metal centers. Eight polydentate Schiff-base ligands have been synthesized with N- and mostly O-based coordination environments which chelate 7-, 8- or 9-coordinate lanthanide ions. The molecular structures were characterized by single crystal X-ray crystallography and the magnetic properties were measured using a SQUID magnetometer. Each chapter consists of crystal structures and magnetic measurements for complexes with the same nuclearity. There are eight DyIII SMMs in this thesis which are discrete molecules that act as magnets below a certain temperature called their blocking temperature. This phenomenon results from an appreciable spin ground state (S) as well as negative uni-axial anisotropy (D), both present in lanthanide ions owing to their f electron shell, generating an effective energy barrier for the reversal of the magnetization (Ueff). The ab initio calculations are also included for the SMMs with high anisotropic energy barriers to understand the mechanisms of slow magnetic relaxation in these systems.

This thesis examined two distinct characteristics of lanthanide and transition metal complexes: Magnetism and Luminescence. In chapter two, synthesis, characterization, magnetic and luminescence investigations of mononuclear lanthanide complexes using Schiff-base tetrazine based ligand were performed. Six novel lanthanide complexes, [LaIIICl3(Htzpy)2], [TbIIICl2(Htzpy)2(MeOH)]Cl, [HoIIICl2(Htzpy)2(MeOH)]Cl, [DyIIICl2(Htzpy)2(MeOH)]Cl, [ErIIICl2(Htzpy)2(MeOH)]Cl and [YbIIICl2(Htzpy)2]Cl have been synthesized successfully and the studies were performed with the application of single crystal X-ray diffractometry, SQUID magnetometry, UV-Vis-NIR spectrometry and custom-built hyperspectral microscope (for luminescence spectroscopy). Chapter three is mainly about the luminescence properties of CoII and CuII complexes using a naphthalimide based ligand. Two complexes, [CoIICl2(Pynap)2] and [CuIIBr2(Pynap)2] were synthesized successfully and characterized using single crystal X-ray diffractometry, UV-Vis spectrometry and hyperspectral microscope (for luminescence spectroscopy). In order to have information about the electrochemical properties of CoII and CuII complexes, their redox activity was monitored by cyclic voltammetry (CV) and compared with the parent ligand. In addition, a rational design to synthesize a new ligand (dipicnap) which consists of both naphthalimide and dipicolinic acid moieties is presented.

Concise overview of synthesis and characterization of single molecule magnets Molecular magnetism is explored as an alternative to conventional solid-state magnetism as the basis for ultrahigh-density memory materials with extremely fast processing speeds. In particular single-molecule magnets (SMM) are in the focus of current research, both because of their intrinsic magnetization properties, as well as because of their potential use in molecular spintronic devices. SMMs are fascinating objects on the example of which one can explain many concepts. Single-Molecule Magnets: Molecular Architectures and Building Blocks for Spintronics starts with a general introduction to single-molecule magnets (SMM), which helps readers to understand the evolution of the field and its future. The following chapters deal with the current synthetic methods leading to SMMs, their magnetic properties and their characterization by methods such as high-field electron paramagnetic resonance, paramagnetic nuclear magnetic resonance, and magnetic circular dichroism. The book closes with an overview of radical-bridged SMMs, which have shown application potential as building blocks for high-density memories. Covers a hot topic – single-molecule magnetism is one of the fastest growing research fields in inorganic chemistry and materials science Provides researchers and newcomers to the field with a solid foundation for their further work Single-Molecule Magnets: Molecular Architectures and Building Blocks for Spintronics will appeal to inorganic chemists, materials scientists, molecular physicists, and electronics engineers interested in the rapidly growing field of study.

This first introduction to the rapidly growing field of molecular magnetism is written with Masters and PhD students in mind, while postdocs and other newcomers will also find it an extremely useful guide. Adopting a clear didactic approach, the authors cover the fundamental concepts, providing many examples and give an overview of the most important techniques and key applications. Although the focus is one lanthanide ions, thus reflecting the current research in the field, the principles and the methods equally apply to other systems. The result is an excellent textbook from both a scientific and pedagogic point of view.

Research on molecule-based magnetic materials was systematized in the 1980s and expanded rapidly. A Special Issue focusing on molecule-based magnetic substances was published in Magnetochemistry. However, the functionalities of the substances increase daily; therefore, the researchers’ quest is not yet in decline. Research on molecule-based magnetism developed across many fields, including chemistry, physics, material chemistry, and applied physics, and the use of the various functionalities of these molecule-based magnetic substances has greatly influenced research on spin-based devices. In honor of Professor Masahiro Yamashita, who contributed greatly to this field, I have put together a Special Issue that highlights ten groundbreaking articles. The issue is entitled, “A Themed Issue of Functional Molecule-Based Magnets: Dedicated to Professor Masahiro Yamashita on the Occasion of his 65th Birthday”. I wish to thank the authors for their dedicated work, and the referees and editorial staff for the time they invested commenting on the articles.

Nanomagnetism is a rapidly expanding area of research which appears to be able to provide novel applications. Magnetic molecules are at the very bottom of the possible size of nanomagnets and they provide a unique opportunity to observe the coexistence of classical and quantum properties. The discovery in the early 90's that a cluster comprising twelve manganese ions shows hysteresis of molecular origin, and later proved evidence of quantum effects, opened a new research area which is still flourishing through the collaboration of chemists and physicists. This book is the first attempt to cover in detail the new area of molecular nanomagnetism, for which no other book is available. In fact research and review articles, and book chapters are the only tools available for newcomers and the experts in the field. It is written by the chemists originators and by a theorist who has been one of the protagonists of the development of the field, and is explicitly addressed to an audience of chemists and physicists, aiming to use a language suitable for the two communities.