Main Group Chemistry at the Interface with Molecular Magnetism

Abstract

Innovative synthetic coordination and, increasingly, organometallic chemistry are at the heart of advances in molecular magnetism. Smart ligand design is essential for implementing controlled modifications to the electronic structure and magnetic properties of transition metal and f-element compounds, and many important recent developments use nontraditional ligands based on low-coordinate main group elements to drive the field forward. This review charts progress in molecular magnetism from the perspective of ligands in which the donor atoms range from low-coordinate 2p elementsparticularly carbon but also boron and nitrogento the heavier p-block elements such as phosphorus, arsenic, antimony, and even bismuth. Emphasis is placed on the role played by novel main group ligands in addressing magnetic anisotropy of transition metal and f-element compounds, which underpins the development of single-molecule magnets (SMMs), a family of magnetic materials that can retain magnetization in the absence of a magnetic field below a blocking temperature. Nontraditional p-block donor atoms, with their relatively diffuse valence orbitals and more diverse bonding characteristics, also introduce scope for tuning the spin−orbit coupling properties and metal−ligand covalency in molecular magnets, which has implications in areas such as magnetic exchange coupling and spin crossover phenomena. The chemistry encompasses transition metals, lanthanides, and actinides and describes recently discovered molecular magnets that can be regarded, currently, as defining the state of the art. This review identifies that main group chemistry at the interface molecular magnetism is an area with huge potential to deliver new types of molecular magnets with previously unseen properties and applications.

Luminescence‐Driven Electronic Structure Determination in a Textbook Dimeric DyIII‐Based Single‐Molecule Magnet

“…On the magnetic aspects, one of the major issue with mononuclear SMMs is the presence of sizable quantum tunnelling of magnetization (QTM) at low temperature, which preventst he openingo ft he magnetic hysteresis loop. [5,32,33] This problem can be solved in minimizing the internal field through either dilution in ad iamagnetic matrix or cancellation of the nuclear spin through isotopice nrichment. [7,[34][35][36][37] Another efficient possibilityi st oc ouple the magnetic centres (superexchange and/ or dipolar interactions) within ap olynuclearedifice.…”

Temperature‐induced formation of two dinuclear dysprosium complexes with different magnetic properties

“…Several efforts have been made thus far to design lanthanide‐based SMMs [especially Dy (III) complex SMMs], and relatively high energy barriers and blocking temperatures (hysteresis temperature) have been achieved . Recent advancements have provided ideas and strategies for designing and synthesizing lanthanide complex SMMs . However, an in‐depth research into the rational design and nature of lanthanide SMMs remains difficult .…”

Redox-Active Dysprosium Single-Molecule Magnet: Spectro-Electrochemistry and Theoretical Investigations

“…For instance, during the last decade, the "through bond" strategy, consisting in the functionalization of the TTF core with organic groups suitable for a coordination reaction with metal precursors [18][19][20][21][22][23][24], has been used to combine lanthanide magnetism and the attractive reversible redox properties of TTF derivatives [25][26][27][28]. Indeed, lanthanide ions possess a strong anisotropy and a large magnetic moment which make them good candidates for obtaining single-molecule magnets (SMMs) [29][30][31][32][33][34][35][36][37]. The motivation to design these new molecular objects is driven by their potential abilities to pave the way for a new generation of quantum devices, such as high-density data storage, quantum computing, and spintronics [38][39][40][41][42][43].…”