Magneto-Structural Correlations in a Series of Pseudotetrahedral [CoII(XR)4]2–Single Molecule Magnets: An ab Initio Ligand Field Study

Suturina, Elizaveta A.; Maganas, Dimitrios; Bill, Eckhard; Atanasov, Mihail; Neese, Frank

doi:10.1021/acs.inorgchem.5b01706

Cited by 107 publications

(137 citation statements)

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“…40 DFT calculations have been employed to extract J values in a linear {Mn II -Mn III -Mn II } cluster [Mn 3 (Hcht) 2 (bpy) 4 ] 3+ (11) (HCht=cis,cis-1,3,5-cyclohexanetriol; see Figure 4b). 45 46 It is worth to note here that this Mn 6 cluster broke the record U eff barrier of the classical Mn 12 Figure 6b) are given in Table 1 and they yield excellent fit to the susceptibility data (see Figure 6c). Calculations in this case clearly suggest that the nextnearest neighbour interactions cannot be neglected as it can be some time strong enough to compete with the nearest-neighbour interactions.…”

Section: Exploring Isotropic J In Mn Polynuclear Complexesmentioning

confidence: 73%

“…The D parameter is particularly associated with Spin-Orbit coupling (SOC), Spin-Spin coupling (SSC) and structural distortion 12 observed in the coordination sphere (such as Jahn-Teller distortion; J-T). These parameters stabilize energy levels with large z-components of the magnetic moment.…”

Section: Introductionmentioning

confidence: 99%

“…In another attempt, calculations were carried out on [Gd III 6 Cu II 12 (OH)12 (L 3 ) 6 (NO 3 ) 7 -(OAc)3 (H 2 O) 12 ](OH)8 (76) 75 {here L 3 = Schiff base ligand, see reference 75 for details) wheel like structure. In another attempt, calculations were carried out on [Gd III 6 Cu II 12 (OH)12 (L 3 ) 6 (NO 3 ) 7 -(OAc)3 (H 2 O) 12 ](OH)8 (76) 75 {here L 3 = Schiff base ligand, see reference 75 for details) wheel like structure.…”

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confidence: 99%

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Modelling spin Hamiltonian parameters of molecular nanomagnets

Gupta

Rajaraman

2016

Chem. Commun.

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Molecular nanomagnets encompass a wide range of coordination complexes possessing several potential applications. A formidable challenge in realizing these potential applications lies in controlling the magnetic properties of these clusters. Microscopic spin Hamiltonian (SH) parameters describe the magnetic properties of these clusters, and viable ways to control these SH parameters are highly desirable. Computational tools play a proactive role in this area, where SH parameters such as isotropic exchange interaction (J), anisotropic exchange interaction (Jx, Jy, Jz), double exchange interaction (B), zero-field splitting parameters (D, E) and g-tensors can be computed reliably using X-ray structures. In this feature article, we have attempted to provide a holistic view of the modelling of these SH parameters of molecular magnets. The determination of J includes various class of molecules, from di- and polynuclear Mn complexes to the {3d-Gd}, {Gd-Gd} and {Gd-2p} class of complexes. The estimation of anisotropic exchange coupling includes the exchange between an isotropic metal ion and an orbitally degenerate 3d/4d/5d metal ion. The double-exchange section contains some illustrative examples of mixed valance systems, and the section on the estimation of zfs parameters covers some mononuclear transition metal complexes possessing very large axial zfs parameters. The section on the computation of g-anisotropy exclusively covers studies on mononuclear Dy(III) and Er(III) single-ion magnets. The examples depicted in this article clearly illustrate that computational tools not only aid in interpreting and rationalizing the observed magnetic properties but possess the potential to predict new generation MNMs.

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Section: Exploring Isotropic J In Mn Polynuclear Complexesmentioning

confidence: 73%

Section: Introductionmentioning

confidence: 99%

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confidence: 99%

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Modelling spin Hamiltonian parameters of molecular nanomagnets

Gupta

Rajaraman

2016

Chem. Commun.

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“…It is to be noted here that we have not considered another important torsional angle parameter of X‐Co‐X‐Y ( ω ) as the ligands here are bidentate in nature and therefore ω does not vary much across the structures. It is observed that the axial and rhombic anisotropies ( D and E / D ) strongly depend on angle 2 θ and dihedral angle θ d …”

Section: Resultsmentioning

confidence: 99%

Magnetic Anisotropy in Co^IIX₄ (X=O, S, Se) Single‐Ion Magnets: Role of Structural Distortions versus Heavy Atom Effect

Sarkar

Tewary

Sinkar

et al. 2019

Chemistry An Asian Journal

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Mononuclearf our coordinate Co II complexes have drawn ag reat deal of attention as they often exhibit excellent single-ion magnet (SIM) properties. Among the reported complexes, the axial zero-field splitting parameter (D)w as found to vary drastically both in terms of the sign as well as strength. There are variousp roposals in this respects uch as structural distortions,h eaviera tom substitution, metalligand covalency,t uning secondary coordination sphere, etc. that are expected to control the D values. To assess the importance of structurald istortions vs. heaviera tom substitution effect, herew eh ave undertaken detailed theoretical studies based on the ab initio CASSCF/NEVPT2 methodt o estimate zero-field splitting parameters for twelve complexes reported in the literature. Our test set includes the {Co II X 4 } (where X = O, S, Se) core structure where the D value was found to vary from + 19 to À118cm À1 .B ased on the structural variation, we have classified the complexes into three types (I-III)w here type I complexes were found to exhibit the largestn egative D value as desired for SIMs. The other two types (II and III)o fc omplexes have been found to be inferior with respect to type I. The secondary coordination spherew as also found to influence D,a ss ubstitution on the secondary coordination sphere atom was found to significantly alter the magnitude of D values. Particularly,t wo structuralp arameters, namely,t he dihedrala ngle between the two ligand planes and the ffX-Co-X polar angle were found to heavily influence the sign and strength of D values. Our analysis clearly reveals that these structural factors are much more important than the heavier atom substitution,o r metal-ligand covalency.Alarge variation in the D and E/D values among these complexesd espite possessing av ery close structuralsimilarity offers an exquisite playground for a chemistt odesign and develop new-generation Co II -based SIMs.

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“…The resulting excitation energies are 952, 4657, and 4703 cm 21 which are very close to previously obtained SORCI values of 954, 4771, and 4771 cm 21 . [48,49] Hence the FIC MRCI method, implemented via the ORCA-AGE or comparable tools, is probably the most rigorous variational post-CASSCF treatment routinely applicable to chemically relevant molecules.…”

Section: Full Papermentioning

confidence: 99%

A toolchain for the automatic generation of computer codes for correlated wavefunction calculations

et al. 2017

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In this work, the automated generator environment for ORCA (ORCA-AGE) is described. It is a powerful toolchain for the automatic implementation of wavefunction-based quantum chemical methods. ORCA-AGE consists of three main modules: (1) generation of "raw" equations from a second quantized Ansatz for the wavefunction, (2) factorization and optimization of equations, and (3) generation of actual computer code. We generate code for the ORCA package, making use of the powerful functionality for wavefunction-based correlation calculations that is already present in the code. The equation generation makes use of the most elementary commutation relations and hence is extremely general. Consequently, code can be generated for single reference as well as multireference approaches and spin-independent as well as spin-dependent operators. The performance of the generated code is demonstrated through comparison with efficient hand-optimized code for some well-understood standard configuration interaction and coupled cluster methods. In general, the speed of the generated code is no more than 30% slower than the hand-optimized code, thus allowing for routine application of canonical ab initio methods to molecules with about 500-1000 basis functions. Using the toolchain, complicated methods, especially those surpassing human ability for handling complexity, can be efficiently and reliably implemented in very short times. This enables the developer to shift the attention from debugging code to the physical content of the chosen wavefunction Ansatz. Automatic code generation also has the desirable property that any improvement in the toolchain immediately applies to all generated code. © 2017 Wiley Periodicals, Inc.

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Magneto-Structural Correlations in a Series of Pseudotetrahedral [Co^II(XR)₄]^2–Single Molecule Magnets: An ab Initio Ligand Field Study

Cited by 107 publications

References 66 publications

Modelling spin Hamiltonian parameters of molecular nanomagnets

Modelling spin Hamiltonian parameters of molecular nanomagnets

Magnetic Anisotropy in Co^IIX₄ (X=O, S, Se) Single‐Ion Magnets: Role of Structural Distortions versus Heavy Atom Effect

A toolchain for the automatic generation of computer codes for correlated wavefunction calculations

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Magneto-Structural Correlations in a Series of Pseudotetrahedral [CoII(XR)4]2–Single Molecule Magnets: An ab Initio Ligand Field Study

Cited by 107 publications

References 66 publications

Modelling spin Hamiltonian parameters of molecular nanomagnets

Modelling spin Hamiltonian parameters of molecular nanomagnets

Magnetic Anisotropy in CoIIX4 (X=O, S, Se) Single‐Ion Magnets: Role of Structural Distortions versus Heavy Atom Effect

A toolchain for the automatic generation of computer codes for correlated wavefunction calculations

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Product

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Magneto-Structural Correlations in a Series of Pseudotetrahedral [Co^II(XR)₄]^2–Single Molecule Magnets: An ab Initio Ligand Field Study

Magnetic Anisotropy in Co^IIX₄ (X=O, S, Se) Single‐Ion Magnets: Role of Structural Distortions versus Heavy Atom Effect