Tuning the Magnetization Dynamic Properties of Nd⋠⋠⋠Fe and Nd⋠⋠⋠Co Single-Molecular Magnets by Introducing 3 d-4 f Magnetic Interactions.

By using paramagnetic [Fe(CN)6 ]3- anions in place of diamagnetic [Co(CN)6 ]3- anions, two field-induced mononuclear single-molecular magnets, [Nd(18-crown-6)(H2 O)4 ][Co(CN)6 ]⋅2 H2 O (1) and [Nd(18-crown-6)(H2 O)4 ][Fe(CN)6 ]⋅2 H2 O (2), have been synthesized and characterized. Single-crystal X-ray diffraction analysis revealed that compounds 1 and 2 were ionic complexes. The NdIII ions were located inside the cavities of the 18-crown-6 ligands and were each bound by four water molecules on either side of the crown ether. Magnetic investigations showed that these compounds were both field-induced single-molecular magnets. By comparing the slow relaxation behaviors of compounds 1 and 2, we found significant differences between the direct and Raman processes for these two complexes, with a stronger direct process in compound 2 at low temperatures. Complete active space self-consistent field (CASSCF) calculations were also performed on two [Nd(18-crown-6)(H2 O)4 ]3+ fragments of compounds 1 and 2. Ab initio calculations showed that the magnetic anisotropies of the NdIII centers in complexes 1 and 2 were similar to each other, which indicated that the difference in relaxation behavior was not owing to the magnetic anisotropy of NdIII . Our analysis showed that the magnetic interaction between the NdIII ion and the low-spin FeIII ion in complex 2 played an important role in enhancing the direct process and suppressing the Raman process of the single-molecular magnet.

Water induced spin-crossover behaviour and magneto-structural correlation in octacyanotungstate(iv)-based iron(ii) complexes.

A series of octacyanotungstate(iv)-based iron(ii) complexes with the general formula Fe(L)8[WIV(CN)8]·nH2O [L = (3-pyridyl)methanol (1, 2), 3-methylpyridine (3), (4-pyridyl)methanol (4), and 4-methylpyridine (5); n = 4 for 1, and n = 0 for 2-5] have been synthesized and characterized. Single crystal X-ray diffraction analysis reveals that the FeII ions lie in the centre of the compressed [FeN6] octahedron in all complexes. FeII and WIV ions are alternately bridged by cyano groups forming a three-dimensional (3D) bimetallic framework. Magnetic investigation shows that 1 displays a gradual spin-crossover (SCO) phenomenon with a spin transition temperature (T1/2) of 200 K, and such SCO behaviour is obviously correlated with the lattice water content of the sample. The magnetic measurements of dehydrated samples show that the fractional conversion from the high-spin (HS) to the low-spin (LS) state is reduced with the increasing of dehydration temperature. Complexes 2-5 are in the HS state and do not exhibit SCO properties in the range of 2-300 K. Comparing the octahedral geometry of [FeN6] of five complexes, quantified by using continuous shape measures, the distortion of complex 1 is the highest as a result of the intermolecular hydrogen bonds, which shorten the Fe-N bond distances and thus increase the ligand field strength at the FeII sites. The analysis of correlations between the structural characteristics and magnetic behaviour of 1-5 suggests that the SCO is mainly tuned by the octahedral distortion of the [FeN6] core caused by intermolecular hydrogen bonds. There is an exact correlation between SCO behaviour and the amount of lattice water molecules existing in the crystal. The spin crossover behaviour of these complexes has been computationally studied using the DFT method. The results of the calculations are consistent with the experiments, which prove that complex 1 with severe distortion of the coordination sphere of FeII is prone to exhibit SCO in theory.

Ferromagnetic Polarization: The Quantum Picture of Switching On/Off Single-Molecule Magnetism.

The mixed 3d-4f pentanuclear complex (Bu4N)[Mn(III)4Y(III)(shi)4(OAc)4(CH3OH)4]·CH3OH·H2O (1) (H3shi = salicylhydroxamic acid) was synthesized by the direct reaction of Y(NO3)3·6H2O, Mn(OAc)2·4H2O, and H3shi. When an additional ligand, (NHBu3)3[W(CN)8]·2H2O, was added, the mixed 3d-4f-5d hexanuclear complex (Et4N)5[Mn(III)4Y(III)(shi)4(OAc)4W(V)(CN)8](WO4)0.5 (2) was obtained. X-ray crystallographic analysis shows that the 3d-4f complex 1 represents a 12-metallacrown-4 (12-MC-4) structure, in which the metallacrown ring [Mn-N-O]4 connection captures one Y(III) ion with four bridging acetate anions, completing the eight-coordinated environment around Y(III) ion, while four methanol molecules each coordinate to the Mn(III) ions on the other side of the Y(III) ion. After octacyanotungstate is introduced, the [W(V)(CN)8] group substitutes for four methanol molecules of 1 to form complex 2. Magnetic studies indicate the overall antiferromagnetic coupling present within the MC ring of complex 1. However, interestingly, the dominant ferromagnetic coupling between Mn(III) ions was observed in complex 2. A susceptibility analysis shows that the natural spin alignments in 12-MC-4 metallacrowns are tuned from overall antiferromagnetic to dominant ferromagnetic fashions by magnetic coupling between Mn(III) ions and the W(V) ion. Complex 1 [Mn(III)4Y(III)] retains an S = 0 ground state, and complex 2 [Mn(III)4Y(III)W(V)] shows obvious single-molecule magnet (SMM) behavior with an ST = 11/2 ground state, respectively, before and after introduction of the octacyanotungstate group. The spin frustration geometrical structure constructed by four Mn(III) ions and one W(V) ion was considered as the key factor for switching on the SMM properties of the 12-MC-4 system.

Two field-induced slow magnetic relaxation processes in a mononuclear Co(ii) complex with a distorted octahedral geometry.

A distorted octahedral Co(II) complex is reported with homoscorpionate ligands. This complex comprised a field-induced single-molecule magnet, showing two slow relaxation processes under a low dc field (<800 Oe) and only one process under a high dc field (≥800 Oe), which was an unusually discovery for 3d metal ions. On the basis of the ac magnetic data, we show for the first time that one of the slow relaxation processes in the low dc field originates from intermolecular dipolar interactions. Interestingly, the Raman process is predominant in the spin reversal relaxation process. The origin of the behaviours of the complex was elucidated by ab initio calculations.

Single-Chain Magnets Based on Octacyanotungstate with the Highest Energy Barriers for Cyanide Compounds.

By introducing large counter cations as the spacer, two isolated 3, 3-ladder compounds, (Ph4P)[Co(II)(3-Mepy)2.7(H2O)0.3W(V)(CN)8] · 0.6H2O (1) and (Ph4As)[Co(II)(3-Mepy)3W(V)(CN)8] (2, 3-Mepy = 3-methylpyridine), were synthesized and characterized. Static and dynamic magnetic characterizations reveal that compounds 1 and 2 both behave as the single-chain magnets (SCMs) with very high energy barriers: 252(9) K for 1 and 224(7) K for 2, respectively. These two compounds display the highest relaxation barriers for cyano-bridged SCMs and are preceded only by two cobalt(II)-radical compounds among all SCMs. Meanwhile, a large coercive field of 26.2 kOe (1) and 22.6 kOe (2) were observed at 1.8 K.

Electrochemical Synthesis and Magnetic Properties of [Cu9W6]: The Ultimate Member of the Quindecanuclear Octacyanometallate-Based Transition-Metal Cluster?

[Cu9W6], synthesized by the electrochemical method, may be the ultimate member of the quindecanuclear octacyanometallate-based transition-metal cluster. Its single-crystal structure and magnetic properties were characterized.

Spin-crossover phenomena of the mononuclear Mn(III) complex tuned by metal dithiolene counteranions.

Three ion-pair complexes based on spin-crossover [Mn(5-Br-sal-N-1,5,8,12)]ClO4 with TBA2[Ni(mnt)2], TBA2[Pt(mnt)2] (mnt = maleonitriledithiolate) and TBA[Ni(dmit)2] respectively (dmit = 2-thioxo-1,3-dithiole-4,5-dithiolato) have been synthesized and structurally characterized. Complexes [Mn(5-Br-sal-N-1,5,8,12)]2[Ni(mnt)2] and [Mn(5-Br-sal-N-1,5,8,12)]2[Pt(mnt)2] are isomorphic and show the axial compression of the octahedral coordination environment of Mn(III) ions. With the temperature increasing the equatorial metal-ligand bond lengths show significant elongation, but the axial bond lengths remain unchanged. Complex [Mn(5-Br-sal-N-1,5,8,12)][Ni(dmit)2]·CH3CN contains π-π, p-π and H-bonds weak interactions. Magnetic investigation shows the spin-crossover phenomena for and , and T1/2 has been increased by 230 K comparing with the reactant complex. However, no spin-crossover was observed in complex , and theoretical calculations show that there are weak antiferromagnetic couplings mediated through π-π interactions.

catena-Poly[[bis-(3-methyl-4-nitro-pyridine N-oxide-κO)cadmium(II)]-di-µ-dicyanamido-κN:N].

In the title compound, [Cd(C(2)N(3))(2)(C(6)H(6)N(2)O(3))(2)](n), the Cd(II) ion (site symmetry ) adopts a distorted trans-CdO(2)N(4) octa-hedral environment, being coordinated by two O-bonded 3-methyl-4-nitro-pyridine N-oxide ligands and four dicyanamide (dca) anions. The bridging dca anions lead to a polymeric chain propagating in [100].