Novel polynuclear architectures incorporating Co2+ and K+ ions bound by dimethylmalonate anions: Synthesis, structure, and magnetic properties

Slow Magnetic Relaxation, Antiferromagnetic Ordering, and Metamagnetism in MnII(H2dapsc)‐FeIII(CN)6Chain Complex with Highly Anisotropic Fe‐CN‐Mn Spin Coupling

“…(2) was calculated in terms of am any-electron superexchange model, [21,22] whichw as applied for the two nonequivalent[ Fe III (CN) 6 ] 3À -Mn II (H 2 dapsc) exchange-coupled pairs involved in the Fe-Mn-Fe asymmetricu nit in the chains of 1 ( Figure S7, (1)) 00000 E( 2 T 2g (2) where the matrix elements (in cm À1 )r efer to the actual wave functions of the three orbitalc omponents 2 T 2g (1-3) (Figure 9 and Ta ble 1) in distorted [Fe(CN) 6 ] 3À complexes involved in the chains of 1.I ti si mportant to note that the structure of the spin-dependent orbitalo perator R differs considerably from that of the widely used Lines model, [23] according to which the ÀRS A S B term in [Eq.…”

“…To get more insighti nto the character of inter-chain interactions in 1,weexplored the mechanism of superexchange interactions between two Mn II (H 2 dapsc)u nits belonging to the neighboring chains, which contact through p-p stacking of planar H 2 dapsc ligands ( Figure S3 a) and through hydrogen bond network incorporating solventw ater molecules and K + cations (Figure S3 b);f or this, we employedt he aforementioned many-electron superexchange theory [21,22] (see the Supporting Information for detail). Our calculations showed that the superexchange mechanism results in av ery weak AF interchain spin coupling between Mn II (H 2 dapsc)m oieties, J' = À0.007 cm À1 for the contacts through p-p stacking (Fig-ure S3 a) and J' = À2.5 10 À4 cm À1 for contactst hrough water molecules (Figure S3 b).…”

“…6 ] 3À )a re magnetically coupled with high-spinm agnetic units carrying no single-ion magnetic anisotropy (Mn II complexes);s uch systems may exhibit interesting sophisticated magnetism as their magnetica nisotropy originatess olely from anisotropic spin coupling. [21,22] Complex 2 is composed of cyano-bridgedp entanuclear molecules with three [Mn II (H 2 dapsc)] 2 + and two [Fe III (CN) 6 ] 3À moieties connected by the trans-CN À ligandso f[ Fe(CN) 6 ]. In the structure 1,i nfinite chainsc onsist of alternating cationic [Mn II (H 2 dapsc)] 2 + and anionic [Fe III (CN) 6 ] 3À units connected by cyanide bridges.…”

Neutral Low-Dimensional Assemblies of a Mn(III) Schiff Base Complex and Octacyanotungstate(V): Synthesis, Characterization, and Magnetic Properties

“…For this purpose we have calculated the JMn-Mn exchange parameter in the [(MnSB + (H2O)]2 moiety ( Figure S6, SI) in terms of a microscopic model based on the multi-electron superexchange theory described in reference [86]; details of such calculations are reported in [87][88][89].…”

Neutral Low-Dimensional Assemblies of a Mn(III) Schiff Base Complex and Octacyanotungstate(V): Synthesis, Characterization and Magnetic Properties

“…The zero-field splitting of Mn III was taken into account using the axial approximation with D term only. Figure S6, SI) in terms of a microscopic model based on the multi-electron superexchange theory described in ref [86]; details of such calculations are reported in [87][88][89].…”