An [FeIII30] molecular metal oxide

Dissolution of FeBr3 in a mixture of acetonitrile and 3,4-lutidine in the presence of an amine results in the formation of an [Fe30] molecular metal oxide containing alternating layers of tetrahedral and octahedral FeIII ions. Mass spectrometry suggests the cluster is formed quickly and remains stable in solution, while magnetic measurements and DFT calculations reveal competing antiferromagnetic exchange interactions.

Oxidation state variation in bis-calix[4]arene supported decametallic Mn clusters

The reaction of MnCl2·4H2O, H8L (2,2’-bis-p-tBu-calix[4]arene) and NEt3 in a dmf/MeOH solvent mixture results in the formation of a mixed valent decametallic cluster of formula [MnII6MnIII4(L)2(µ3-OH)4(µ-OH)4(MeOH)4(dmf)4(MeCN)2]·MeCN (3). Complex 3 crystallises in the monoclinic space group P21/n with the asymmetric unit comprising half of the compound. Structure solution reveals that the bis-calix[4]arene ligands are arranged such that one TBC[4] moiety in each has undergone inversion in order to accommodate a [MnIII4MnII6] metallic skeleton that describes three vertex-sharing [MnIII2MnII2] butterflies. The structure is closely related to the species [MnIII6MnII4(L)2(μ3-O)2(μ3-OH)2(μ-OMe)4(H2O)4(dmf)8]·4dmf (4), the major difference being the oxidation level of the Mn ions in the core of the compound. DFT calculations on the full structures reveal that replacing the MnIII ions in 4 for MnII ions in 3 results in a significant decrease in the magnitude of some antiferromagnetic exchange contributions, a switch from ferromagnetic to antiferromagnetic in others, and the loss of significant spin frustration.

A Multifunctional 3D Supermolecular Co Coordination Polymer With Potential for CO2 Adsorption, Antibacterial Activity, and Selective Sensing of Fe3+/Cr3+ Ions and TNP

A 3D supermolecular structure [Co3(L)2 (2,2′-bipy)2](DMF)3(H2O)3 1) (H3L = 4,4′,4″-nitrilotribenzoic acid) has been constructed based on H3L, and 2,2′-bipy ligands under solvothermal conditions. Compound 1 can be described as a (3, 6)-connected kgd topology with a Schläfli symbol (43)2(46.66.83) formed by [Co3(CO2)6] secondary building units. The adsorption properties of the activated sample 1a has been studied; the result shows that 1a has a high adsorption ability: the CO2 uptakes were 74 cm3·g−1 at 273 K, 50 cm3·g−1 at 298 K, the isosteric heat of adsorption (Qst) is 25.5 kJ mol−1 at zero loading, and the N2 adsorption at 77 K, 1 bar is 307 cm3 g−1. Magnetic measurements showed the existence of an antiferromagnetic exchange interaction in compound 1, besides compound 1 exhibits effective luminescent performance for Fe3+/Cr3+ and TNP.

[(VIVO)2MII5] (M = Ni, Co) Anderson Wheels

Heterometallic Anderson wheels of formula [(VIVO)2MII5(hmp)10Cl2](ClO4)2·2MeOH (M = Ni, 1; Co, 2) have been synthesised from the solvothermal reaction of M(ClO4)2·6H2O and VCl3 with hmpH (2-(hydroxymethyl)pyridine). The metallic skeleton describes a centred hexagon, with the two vanadyl ions sitting on opposing sides of the outer ring. Magnetic susceptibility and magnetisation measurements indicate the presence of both ferromagnetic and antiferromagnetic exchange interactions. Theoretical calculations based on density functional methods reproduce both the sign and strength of the exchange interactions found experimentally, and rationalise the parameters extracted.

[(VIVO)2MII5] (M = Ni, Co) Anderson Wheels

Heterometallic Anderson wheels of formula [(VIVO)2MII5(hmp)10Cl2](ClO4)2·2MeOH (M = Ni, 1; Co, 2) have been synthesised from the solvothermal reaction of M(ClO4)2·6H2O and VCl3 with hmpH (2-(hydroxymethyl)pyridine). The metallic skeleton describes a centred hexagon, with the two vanadyl ions sitting on opposing sides of the outer ring. Magnetic susceptibility and magnetisation measurements indicate the presence of both ferromagnetic and antiferromagnetic exchange interactions. Theoretical calculations based on density functional methods reproduce both the sign and strength of the exchange interactions found experimentally, and rationalise the parameters extracted.

Effect of the Alkaline Metal Ion on the Crystal Structure and Magnetic Properties of Heterometallic GdIII-VIV Complexes Based on Cyclobutane-1,1-dicarboxylate Anions

A series of heterometallic GdIII–VIV compounds were synthesized by the reaction of VOSO4·3H2O with cyclobutane-1,1-dicarboxylic acid salts M2(cbdc) (M = Na, Rb, Cs). The new compounds were formed by [Gd(VO)2(сbdc)4(H2O)8]− trinuclear anionic units that were similar in composition but differed in structure, depending on the nature of the alkali metal cation incorporated in the crystal structure of the compound. In the case of Na+, the {GdV2}– units were characterized by identical V···Gd distances and were linked into the 1D-polymeric chain [NaGd(VO)2(cbdc)4(H2O)10]n (1). In the systems with Rb+ and Cs+, the V···Gd distances were different, and the {GdV2}– units were linked into the 3D-framework {[RbGd(VO)2(cbdc)4(H2O)10]·2.5H2O}n (2) and the octanuclear molecule {[CsGd(VO)2(cbdc)4(H2O)11]·5H2O}2 (3), respectively. According to dc-magnetic measurements, the VIV and GdIII ions were ferromagnetically coupled in compound 1 (JVGd = 0.163 ± 0.008 cm−1), while in compounds 2 and 3, ferro- and weak antiferromagnetic exchange interactions were observed (JVGd = 0.989 ± 0.028 and −0.089 ± 0.008 cm−1 for 2, 0.656 ± 0.009 and −0.050 ± 0.004 cm−1 for 3). Analysis of the EPR spectra of 1 revealed the presence of weak magnetic anisotropy of GdIII ions (D~0.08 cm−1 and E/D~0.1–0.15). Ac-susceptibility measurements showed an occurrence the field-induced slow relaxation of magnetization in 1–3.

Ferromagnetic and spin-glass like transition in the q-neighbor Ising model on random graphs

The q-neighbor Ising model is investigated on homogeneous random graphs with a fraction of edges associated randomly with antiferromagnetic exchange integrals and the remaining edges with ferromagnetic ones. It is a nonequilibrium model for the opinion formation in which the agents, represented by two-state spins, change their opinions according to a Metropolis-like algorithm taking into account interactions with only a randomly chosen subset of their q neighbors. Depending on the model parameters in Monte Carlo simulations, phase diagrams are observed with first-order ferromagnetic transition, both first- and second-order ferromagnetic transitions and second-order ferromagnetic and spin-glass-like transitions as the temperature and fraction of antiferromagnetic exchange integrals are varied; in the latter case, the obtained phase diagrams qualitatively resemble those for the dilute spin-glass model. Homogeneous mean-field and pair approximations are extended to take into account the effect of the antiferromagnetic exchange interactions on the ferromagnetic phase transition in the model. For a broad range of parameters, critical temperatures for the first- or second-order ferromagnetic transition predicted by the homogeneous pair approximation show quantitative agreement with those obtained from Monte Carlo simulations; significant differences occur mainly in the vicinity of the tricritical point in which the critical lines for the second-order ferromagnetic and spin-glass-like transitions meet. Graphic abstract

Tetranuclear copper(ii) cubane complexes derived from self-assembled 1,3-dimethyl-5-(o-phenolate-azo)-6-aminouracil: structures, non-covalent interactions and magnetic property

A new doubly opened 4 + 2 Cu4O4 cubane cluster exhibits strong antiferromagnetic exchange coupling with J1 = −110.1 cm−1, and J2 = −27.1 cm−1.