Magnetic Structure of the Large-Spin Mn₁₀ and Mn₁₉ Complexes: A Theoretical Complement to an Experimental Milestone

Abstract

High-spin molecules have been proposed as candidates for the storage of information at the molecular level. The electronic structure of two complex magnetic molecular systems, Mn 10 and Mn 19, is characterized by means of a computational study based on density functional theory. All the exchange interactions in the recently reported Mn 19 complex with the highest known spin value of 83/2, and in its highly symmetric Mn 10 parent compound, are ferromagnetic. In these complexes, there are two kinds of ferromagnetic coupling: the first one corresponds to Mn (II)-Mn (III) interactions through a double mu 2-alkoxo-mu 4-oxo bridge where the high coordination number of the Mn (II) cations results in long Mn (II)-O bond distances, while the second one involves Mn (III)-Mn (III) interactions through mu 2-alkoxo-mu 3-eta (1):eta (1):eta (1) azido bridging ligands with long Mn (III)-N distances due to a Jahn-Teller effect.

Modelling spin Hamiltonian parameters of molecular nanomagnets

“…Based on the structural topology from three exchange to eight different exchange been assumed in these clusters. 52 There are several DFT studies on the magnetic coupling in dodecametallic Mn clusters. Among the structures studied, only one exchange is found between Mn III -Mn III pairs (mediated via µ 2 -F and µ 3 -O{teaH 2-} motif) and this exchange is computed to be weakly ferromagnetic.…”

Interpretation and Prediction of Properties of Transition Metal Coordination Compounds

“…D; spin S, zero-field splitting D). However, much progress has been made in the computation of isotropic and anisotropic exchange coupling parameters [144][145][146]. The major problem in developing higher temperature SMMs is a limited understanding of the local single ion and the total magnetic anisotropies, D, and their dependence on the local and global geometries [16,[147][148][149][150].…”

Synthesis, structure, and magnetic properties of a tetradecanuclear manganese complex

“…The synthesis and characterization of 3d transition metal complexes with various nuclearities and structure topologies are of interest because of their fascinating physical properties and interesting structures [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18]. The uses of suitable types of ligands and appropriate reaction conditions have allowed the formation of a variety of high nuclear complexes.…”

“…The uses of suitable types of ligands and appropriate reaction conditions have allowed the formation of a variety of high nuclear complexes. There are many examples of high nuclearities in the field of manganese chemistry [6][7][8][9][10][11][12][13][14][15][16][17]. The synthesis of such complexes involves the use of multinuclear clusters as starting materials.…”