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The cationic complexes of Mn(III) with the 5-Hal-sal2323 (Hal = Cl, Br) ligands and a paramagnetic doubly charged counterion [ReCl6]2− have been synthesized: [Mn(5-Cl-sal2323)]2[ReCl6] (1) and [Mn(5-Br-sal2323)]2[ReCl6] (2). Their crystal structures and magnetic properties have been studied. These isostructural two-component ionic compounds show a thermally induced spin transition at high temperature associated with the cationic subsystem and a field-induced slow magnetic relaxation of magnetization at cryogenic temperature, associated with the anionic subsystem. The compounds are the first examples of the coexistence of spin crossover and field-induced slow magnetic relaxation in the family of known [MnIII(sal2323)] cationic complexes with various counterions. [ABSTRACT FROM AUTHOR]

Three tetraphenylborates of mononuclear Mn(III) cation complexes with hexadentate ligands, the products of the reaction between a N,N′‐bis(3‐aminopropyl)ethylenediamine and salicylaldehydes with the different haloid substitutions at the 5 or 3,5 positions, have been synthesized: [Mn(5‐F‐sal‐N‐1,5,8,12)]BPh4 (1), [Mn(3,5‐diCl‐sal‐N‐1,5,8,12)]BPh4 (2) and [Mn(3,5‐Br,Cl‐sal‐N‐1,5,8,12)]BPh4 (3). Their crystal structure, dielectric constant (ϵ) and magnetic properties have been studied. Ligand substituents have a dramatic effect on the structure and magnetic properties of the complexes. With decreasing temperature, the complex (1) shows a gradual spin crossover from the high‐spin state (HS) to the HS:LS intermediate phase, followed by an abrupt transition to the low‐spin state (LS) without changing the crystal symmetry. The complexes 2 and 3 are isostructural, but have fundamentally different properties. Complex 2 demonstrates two structural phase transitions related to sharp spin crossovers from the HS to the HS:LS intermediate phase at 137 K and from the intermediate phase to the LS at 87 K, while complex 3 exhibits only one spin transition from the HS to the HS:LS intermediate phase at 83 K. [ABSTRACT FROM AUTHOR]

A series of three mononuclear pentagonal-bipyramidal V(III) complexes with the equatorial pentadentate N3O2 ligand (2,6-diacethylpyridinebis(benzoylhydrazone), H2DAPBH) in the different charge states (H2DAPBH0, HDAPBH1−, DAPBH2−) and various apical ligands (Cl−, CH3OH, SCN−) were synthesized and characterized structurally and magnetically: [V(H2DAPBH)Cl2]Cl·C2H5OH (1), [V(HDAPBH)(NCS)2]·0.5CH3CN·0.5CH3OH (2) and [V(DAPBH)(CH3OH)2]Cl·CH3OH (3). All three complexes reveal paramagnetic behavior, resulting from isolated S = 1 spins with positive zero-field splitting energy expected for the high-spin ground state of the V3+ (3d2) ion in a PBP coordination. Detailed high-field EPR measurements for compound 3 show that its magnetic properties are best described by using the spin Hamiltonian with the positive ZFS energy (D = +4.1 cm−1) and pronounced dimer-like antiferromagnetic spin coupling (J = −1.1 cm−1). Theoretical analysis based on superexchange calculations reveals that the long-range spin coupling between distant V3+ ions (8.65 Å) is mediated through π-stacking contacts between the planar DAPBH2− ligands of two neighboring [V(DAPBH)(CH3OH)2]+ complexes. [ABSTRACT FROM AUTHOR]

Reactions of [Mn(H2dapsc)Cl2]⋅H2O (dapsc=2,6‐ diacetylpyridine bis(semicarbazone)) with K3[Fe(CN)6] and (PPh4)3[Fe(CN)6] lead to the formation of the chain polymeric complex {[Mn(H2dapsc)][Fe(CN)6][K(H2O)3.5]}n⋅1.5n H2O (1) and the discrete pentanuclear complex {[Mn(H2dapsc)]3[Fe(CN)6]2(H2O)2}⋅4 CH3OH⋅3.4 H2O (2), respectively. In the crystal structure of 1 the high‐spin [MnII(H2dapsc)]2+ cations and low‐spin hexacyanoferrate(III) anions are assembled into alternating heterometallic cyano‐bridged chains. The K+ ions are located between the chains and are coordinated by oxygen atoms of the H2dapsc ligand and water molecules. The magnetic structure of 1 is built from ferrimagnetic chains, which are antiferromagnetically coupled. The complex exhibits metamagnetism and frequency‐dependent ac magnetic susceptibility, indicating single‐chain magnetic behavior with a Mydosh‐parameter φ=0.12 and an effective energy barrier (Ueff/kB) of 36.0 K with τ0=2.34×10−11 s for the spin relaxation. Detailed theoretical analysis showed highly anisotropic intra‐chain spin coupling between [FeIII(CN)6]3− and [MnII(H2dapsc)]2+ units resulting from orbital degeneracy and unquenched orbital momentum of [FeIII(CN)6]3− complexes. The origin of the metamagnetic transition is discussed in terms of strong magnetic anisotropy and weak AF interchain spin coupling. [ABSTRACT FROM AUTHOR]

[Display omitted] • A new bicomponent [MnIII(5-F-sal 2 323)] 2 [ReIVCl 6 ] complex was synthesized and its crystal structure and magnetic properties were studied. • The complex exhibits no spin transition and field-induced single-ion magnetism associated with the cationic and anionic subsystems, respectively, unlike Cl- and Br-substituted analogues, which demonstrate these properties. • The nature of the halogen in the 5-position of the phenyl ring has no effect on the value of the energy gap between the LS and HS states of the Mn(III) complexes with sal 2 323 ligand. • The stabilization of the HS state and the suppression of single-ion magnetism in the F-substituted complex are associated with a strong π-π stacking between the phenyl rings of Mn cations in H-bonded chain and shortened Mn...Re and Re...Re distances, respectively. A complex [Mn(5-F-sal 2 323)] 2 [ReCl 6 ] was synthesized and its crystal structure and magnetic properties were studied in comparison with complexes [Mn(5-Cl-sal 2 323)] 2 [ReCl 6 ] and [Mn(5-Br-sal 2 323)] 2 [ReCl 6 ] showing spin crossover and field-induced single-ion magnetism. [ABSTRACT FROM AUTHOR]