Role of Ab Initio Calculations in the Design and Development of Organometallic Lanthanide‐Based Single‐Molecule Magnets

Abstract

Single‐molecule magnets based on lanthanides are very attractive due to their potential applications proposed in the area of microelectronic devices. Very recent advances in this area are due to the blend of conventional lanthanide chemistry with organometallic ligands, and several breakthrough achievements are attained with this combination. Ab initio methods based on multi‐reference CASSCF calculations are playing a vital role in the design and development of such molecules. In this minireview, we aim to appraise various contributions in the area of organometallic lanthanide complexes (those containing lanthanide‐carbon bonds) and describe how these robust wavefunction‐based methods have played a constructive role not only in rationalizing the observed magnetic properties but also proven to be a potential predictive tool with some selected examples.

A General Strategy for Hollow Metal‐Phytate Coordination Complex Micropolyhedra Enabled by Cation Exchange

“…The unexpected results may be explained by the presence of deeply buried 4f‐orbitals for these Ln 3+ ions. The deeply buried 4f‐orbitals usually have difficulty in the formation of coordination bonds, giving rise to a decreased Lewis acidity [18] . In fact, this argument is supported by the fact that these Ln 3+ ions have electronegativity in the range of 1.27–1.30, smaller than that of Co 2+ ions (1.47) [19] …”

The coexistence of longτQTMand highUeffas a concise criterion for a good single-molecule magnet: a theoretical case study of square antiprism dysprosium single-ion magnets

“…[2][3][4][5][6][7][8][9]36,37 Nowadays, theoretical study is important to this understanding and its value has been widely acknowledged. [2][3][4][38][39][40][41][42][43] As a representative type of theoretical study, multi-configurational ab initio calculations are capable of providing important information on SMMs, e.g., spin Hamiltonian parameters, via the accurate description of the electronic structure of the system. 3,38,41,[44][45][46][47][48][49][50] Actually, ab initio calculations have become one of the most popular tools to interpret experimental results and to provide a strategic guide in current researches of SMMs.…”

“…3,38,41,[44][45][46][47][48][49][50] Actually, ab initio calculations have become one of the most popular tools to interpret experimental results and to provide a strategic guide in current researches of SMMs. 3,10,[38][39][40][41]43,48,49,[51][52][53][54][55][56][57][58][59][60][61][62][63][64][65][66] One recent area of theoretical progress is the reliable prediction of some key parameters of the magnetic relaxation of SMMs based on ab initio calculations. 7,9,[67][68][69] Thus, the direct comparison between theoretical predictions and experimental results becomes feasible for SMMs.…”

“…2–9,36,37 Nowadays, theoretical study is important to this understanding and its value has been widely acknowledged. 2–4,38–43 As a representative type of theoretical study, multi-configurational ab initio calculations are capable of providing important information on SMMs, e.g. , spin Hamiltonian parameters, via the accurate description of the electronic structure of the system.…”

A General Strategy for Hollow Metal‐Phytate Coordination Complex Micropolyhedra Enabled by Cation Exchange

“…Theu nexpected results may be explained by the presence of deeply buried 4f-orbitals for these Ln 3+ ions.T he deeply buried 4f-orbitals usually have difficulty in the formation of coordination bonds,g iving rise to ad ecreased Lewis acidity. [18] In fact, this argument is supported by the fact that these Ln 3+ ions have electronegativity in the range of 1.27-1.30, smaller than that of Co 2+ ions (1.47). [19] We further examined the cation exchange of the Co 2+ -PA polyhedral networks with soft-acid M n+ ions,i ncluding Ca 2+ and Sr 2+ .Asexpected, they showed weaker exchange strength in comparison to transition M n+ ions with the exception of Ni 2+ ions (Figure 3a;F igures S25-S27, Table S5).…”