Self-Assembly and Magnetic Order of Bi-Molecular 2D Spin Lattices of M(II,III) Phthalocyanines on Au(111)

Abstract

Single layer low-dimensional materials are presently of emerging interest, including in the context of magnetism. In the present report, on-surface supramolecular architecturing was further developed and employed to create surface supported two-dimensional binary spin arrays on atomically clean non-magnetic Au(111). By chemical programming of the modules, different checkerboards were produced combining phthalocyanines containing metals of different oxidation and spin states, diamagnetic zinc, and a metal-free ‘spacer’. In an in-depth, spectro-microscopy and theoretical account, we correlate the structure and the magnetic properties of these tunable systems and discuss the emergence of 2D Kondo magnetism from the spin-bearing components and via the physico-chemical bonding to the underlying substrate. The contributions of the individual elements, as well as the role of the electronic surface state in the bottom substrate, are discussed, also looking towards further in-depth investigations.

A Review of the Current State of Magnetic Force Microscopy to Unravel the Magnetic Properties of Nanomaterials Applied in Biological Systems and Future Directions for Quantum Technologies

“…DPN could be also employed to precisely control the deposition on the customized nanoconstrictions of other magnetic biomolecules like the aforementioned porphyrins or matter of different a nature such as metalloenzymes, or small magnetosome nanoparticles. Moreover, the creation of 2D- and 3D-lattice architectures of nanometric magnetic features can make tunable systems by out-of-plane ligation by scanning probes [ 368 ].…”

Guiding the Formation of Metal–Organic Structures of 1,4-Diaminoanthraquinone through Surface-Based Cu Atoms

“…The formation of two-dimensional (2D) metal–organic structure on surfaces comprising organic ligands and metal centers has recently become a subject of active research interest due to its potential applications in different fields ranging from surface patterning, heterogeneous catalysis, magnetism, and host–guest chemistry. − The metal–organic coordination bond, as a carrier of the metal–organic structure, is a noncovalent bond formed through the interaction between an organic ligand that provides lone pair electrons and a metal atom or ion that provides empty orbitals. − In studies, organic molecules with functional groups containing lone pair electrons such as O, N, and S are commonly used as ligands, while transition metals mainly provide vacant orbitals. − Moreover, the synthesis and development of coordination structures are influenced by the strength of interactions between the constituents and the underlying substrate. − The substrate’s role in overlayer growth is significant, as it can serve as metal coordination centers by providing native adatoms or induce surface reconstructions when its influence is strong. ,,− In addition, the introduction of foreign metal atoms on inert metal surfaces provides a pathway for the construction of a more diverse and interesting metal-coordination structure. − Therefore, gradually guiding the formation of stable metal–organic structures through the introduction of foreign atoms or the selection of metal surfaces for a molecule with special morphology and function would be beneficial for gaining a deeper understanding of the competitive relationship between molecules, metal atoms, and surfaces in surface structural construction. − 1,4-Diaminoanthraquinone (DAQ) with amino and carbonyl groups arranged in a symmetrical distribution is an important organic ligand due to its versatile coordination behavior and interesting electronic properties. It can form stable complexes with various metal ions, enabling the design and synthesis of novel metal–organic complex .…”

Manipulation of the Magnetic State of a Porphyrin-Based Molecule on Gold: From Kondo to Quantum Nanomagnet via the Charge Fluctuation Regime

“…Among the most studied classes of magnetic molecules are the transition metal phthalocyanine (Pc) and porphyrin (P) families, which are easily deposited at the surface in a vacuum and studied by various local probe microscopies and spectroscopies. In these molecules, the spin state is mainly given by the spin polarization of the central transition metal ion d states. , Several works have focused on the influence of external parameters on the magnetic ground state such as the influence of charge transfer to the orbitals of the molecule, − the effect of surface spin–orbit coupling and magnetic anisotropy, , the coupling to the substrate, ,− the interaction with attached and neighboring molecules, , the structural deformation, , or the chemical substitution of ligands . For all of these studies, a systematic understanding of the effect of mixed valence and charge fluctuations is still missing, although they have a strong influence on the effect of magnetic anisotropy.…”