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Abstraction of iodide from [(η5‐C5iPr5)2UI] (1) produced the cationic uranium(III) metallocene [(η5‐C5iPr5)2U]+ (2) as a salt of [B(C6F5)4]−. The structure of 2 consists of unsymmetrically bonded cyclopentadienyl ligands and a bending angle of 167.82° at uranium. Analysis of the bonding in 2 showed that the uranium 5f orbitals are strongly split and mixed with the ligand orbitals, thus leading to non‐negligible covalent contributions to the bonding. Investigation of the dynamic magnetic properties of 2 revealed that the 5f covalency leads to partially quenched anisotropy and fast magnetic relaxation in zero applied magnetic field. Application of a magnetic field leads to dominant relaxation by a Raman process. [ABSTRACT FROM AUTHOR]

Abstraction of iodide from [(η5‐C5iPr5)2UI] (1) produced the cationic uranium(III) metallocene [(η5‐C5iPr5)2U]+ (2) as a salt of [B(C6F5)4]−. The structure of 2 consists of unsymmetrically bonded cyclopentadienyl ligands and a bending angle of 167.82° at uranium. Analysis of the bonding in 2 showed that the uranium 5f orbitals are strongly split and mixed with the ligand orbitals, thus leading to non‐negligible covalent contributions to the bonding. Investigation of the dynamic magnetic properties of 2 revealed that the 5f covalency leads to partially quenched anisotropy and fast magnetic relaxation in zero applied magnetic field. Application of a magnetic field leads to dominant relaxation by a Raman process. [ABSTRACT FROM AUTHOR]

The pentagonal bipyramidal single-ion magnets (SIMs) are among the most attractive prototypes of high-performance single-molecule magnets (SMMs). Here, a fluorescence-active phosphine oxide ligand CyPh2PO (=cyclohexyl(diphenyl)phosphine oxide) was introduced into [Dy(CyPh2PO)2(H2O)5]Br3⋅2 (CyPh2PO)⋅EtOH⋅3 H2O, and combined dynamic magnetic measurement, optical characterization, ab initio calculation, and magneto-optical correlation of this high-performance pseudo- D5 h DyIII SIM with large Ueff (508(2) K) and high magnetic hysteresis temperature (19 K) were performed. This work provides a deeper insight into the rational design of promising molecular magnets. [ABSTRACT FROM AUTHOR]

An extremely rare non-Kramers holmium(III) single-ion magnet (SIM) is reported to be stabilized in the pentagonal-bipyramidal geometry by a phosphine oxide with a high energy barrier of 237(4) cm−1. The suppression of the quantum tunneling of magnetization (QTM) at zero field and the hyperfine structures originating from field-induced QTMs can be observed even from the field-dependent alternating-current magnetic susceptibility in addition to single-crystal hysteresis loops. These dramatic dynamics were attributed to the combination of the favorable crystal-field environment and the hyperfine interactions arising from 165Ho ( I=7/2) with a natural abundance of 100 %. [ABSTRACT FROM AUTHOR]

The area of molecular magnetic coolants has developed rapidly in recent years. A large number of competitive candidates have been reported, with the cooling performances chasing each other. In this account, four explicit strategies, namely, increasing ground-state spin, reducing magnetic anisotropy, weakening magnetic interactions, and lowering the molecular weight, are proposed from the theoretical viewpoint towards improving the magnetocaloric effect (MCE). According to this guidance, these successful strategies are discussed to pursue excellent magnetic coolants. This is accompanied by a discussion of the representative examples reported by our group. The magnetic entropy change increases from one compound to another, which in the most pronounced cases is suggestive of being the largest MCE in magnetic coolants. [ABSTRACT FROM AUTHOR]

A Hoffman-like coordination polymer with appreciable porosity and uncoordinated pyridyl groups, namely, [Fe(2,5-bpp){Au(CN)2}2] ⋅ x Solv (2,5-bpp=2,5-bis(pyrid-4-yl)pyridine; Solv=solvent), was synthesised and characterised. A series of fascinating spin-crossover behaviours with abrupt, stepwise and hysteretic features were obtained by exchange with a range of protic solvents (ethanol, n-propanol, isopropyl alcohol, sec-butanol and isobutanol). Guest-host hydrogen-bonding interactions involving the H-accepting site of the framework are primarily responsible for the pronounced cooperativity of these spin-crossover behaviours. Meanwhile, the tunable critical temperatures over a range of about 130 K are presumably attributable to a certain degree of competition between internal pressure and local electronic influences of solvents. [ABSTRACT FROM AUTHOR]

The transformation of MnII glycolates (glc) between the three-dimensional coordination polymer [Mn(glc)2] n ( 1) and discrete mononuclear phase [Mn(glc)2(H2O)2] ( 2) can be reversibly switched by water molecules, which dramatically change the magnetocaloric effect (MCE) of MnII glycolates from the maximum of 6.9 J kg−1 K−1 in 1 to 60.3 J kg−1 K−1 in 2. This case example reveals that the effect of magnetic coupling on MCE plays a dominant role over that of other factors such as magnetic density for 3d-type magnetic refrigerants. [ABSTRACT FROM AUTHOR]

The comprehensive study reported herein provides compelling evidence that anion templates are the main driving force in the formation of two novel nanoscale lanthanide hydroxide clusters, {Gd38(ClO4)6} ( 1) and {Gd48Cl2(NO3)} ( 2), characterized by single-crystal X-ray crystallography, infrared spectroscopy, and magnetic measurements. {Gd38(ClO4)6}, encapsulating six ClO4− ions, features a cage core composed of twelve vertex-sharing {Gd4} tetrahedrons and one Gd⋅⋅⋅Gd pillar. When Cl− and NO3− were incorporated in the reaction instead of ClO4−, {Gd48Cl2(NO3)} is obtained with a barrel shape constituted by twelve vertex-sharing {Gd4} tetrahedrons and six {Gd5} pyramids. What is more, the cage-like {Gd38} can be dynamically converted into the barrel-shaped {Gd48} upon Cl− and NO3− stimulus. To our knowledge, it is the first time that the linear M-O-M′ fashion and the unique μ8-ClO4− mode have been crystallized in pure lanthanide complex, and complex 2 represents the largest gadolinium cluster. Both of the complexes display large magnetocaloric effect in units of J kg−1 K−1 and mJ cm−3 K−1 on account of the weak antiferromagnetic exchange, the high NGd/ MW ratio (magnetic density), and the relatively compact crystal lattice (mass density). [ABSTRACT FROM AUTHOR]

Two kinds of inorganic gadolinium(III)-hydroxy 'ladders', [2× n] and [3× n], were successfully trapped in succinate (suc) coordination polymers, [Gd2(OH)2(suc)2(H2O)] n ⋅ 2 n H2O ( 1) and [Gd6(OH)8(suc)5(H2O)2] n ⋅4 n H2O ( 2), respectively. Such coordination polymers could be regarded as alternating inorganic-organic hybrid materials with relatively high density. Magnetic and heat capacity studies reveal a large cryogenic magnetocaloric effect (MCE) in both compounds, namely (Δ H=70 kG) 42.8 J kg−1 K−1 for complex 1 and 48.0 J kg−1 K−1 for complex 2. The effect of the high density is evident, which gives very large volumetric MCEs up to 120 and 144 mJ cm−3 K−1 for complexes 1 and 2, respectively. [ABSTRACT FROM AUTHOR]

The pentagonal bipyramidal single‐ion magnets (SIMs) are among the most attractive prototypes of high performance single‐molecule magnets (SMMs). A fluorescence‐active phosphine oxide ligand is introduced, and by combining dynamic magnetic measurements, optical characterization, and ab initio calculations, the magneto‐optical correlation of a high‐performance pseudo‐D5h DyIII SIM with large Ueff = 508(2) K and high magnetic hysteresis temperature of 19 K, [Dy(CyPh2PO)2(H2O)5]Br3⋅2 (CyPh2PO)⋅EtOH⋅3 H2O (CyPh2PO=cyclohexyl(diphenyl)phosphine oxide) was studied. This work provides a deeper insight into the rational design of promising molecular magnets. More information can be found in the Full Paper by M.‐L. Tong, J.‐L. Liu, et al. on page 5708 ff. [ABSTRACT FROM AUTHOR]

Review: [20 refs. [ABSTRACT FROM AUTHOR]

A series of heterometallic 3d-Gd3+ complexes based on a lanthanide metalloligand, [M(H2O)6][Gd(oda)3] ⋅3 H2O [M=Cr3+ ( 1-Cr)] (H2oda=2,2′-oxydiacetic acid), [M(H2O)6][MGd(oda)3]2 ⋅3 H2O [M=Mn2+ ( 2-Mn), Fe2+ ( 2-Fe) and Co2+ ( 2-Co)], and [M3Gd2(oda)6(H2O)6] ⋅12 H2O [M=Ni2+ ( 3-Ni), Cu2+ ( 3-Cu), and Zn2+ ( 3-Zn)], are reported. Magnetic and heat-capacity studies revealed a significant impact on the magnetocaloric effect depending on the anisotropy of the 3d transition metal ions, as confirmed by comparison of the observed maximum values of −Δ Sm between complexes 2-Co and 1-Cr. In these two complexes, the 3d metal ions have the same spin ( S=3/2 for Co2+ and Cr3+ ions), and the theoretical calculation suggested a larger −Δ Sm value for 2-Co (47.8 J K−1 kg−1) than 1-Cr (37.5 J K−1 kg−1); however, the significant anisotropy of Co2+ ions in 2-Co, which can result in smaller effective spins, gives a smaller value of −Δ Sm for 2-Co (32.2 J K−1 kg−1) than for 1-Cr (35.4 J K−1 kg−1) at Δ H=9 T. [ABSTRACT FROM AUTHOR]

Based on the analogous kagomé [Co3(imda)2] layers (imda=imidazole-4,5-dicarboxylate), a family of pillar-layered frameworks with the formula of [Co3(imda)2(L)3] ⋅(L) n ⋅ xH2O ( 1: L=pyrazine, n=0, x=8; 2: L=4,4′-bipyridine, n=1, x=8; 3: L=1,4-di(pyridin-4-yl)benzene, n=1, x=13; 4: L=4,4′-di(pyridin-4-yl)-1,1′-biphenyl, n=1, x=14) have been successfully synthesized by a hydrothermal/solvothermal method. Single-crystal structural analysis shows a significant increase in the interlayer distances synchronized with the extension of the pillar ligands, namely, 7.092(3) ( 1), 10.921(6) ( 2), 14.780(5) ( 3), and 19.165(4) Å ( 4). Despite the wrinkled kagomé layers in complexes 2- 4, comprehensive magnetic characterizations revealed weakening of interlayer magnetic interactions and an increase in the degree of frustration as the pillar ligand becomes longer from 1 to 4; this leads to characteristic magnetic ground states. For compound 4, which has the longest interlayer distance, the interlayer interaction is so weak that the magnetic properties observed within the range of temperature measured would correspond to the frustrated layer. [ABSTRACT FROM AUTHOR]

A record anisotropy barrier (319 cm−1) for all d-f complexes was observed for a unique FeII-DyIII-FeII single-molecule magnet (SMM), which possesses two asymmetric and distorted FeII ions and one quasi- D5 h DyIII ion. The frozen magnetization of the DyIII ion leads to the decreased FeII relaxation rates evident in the Mössbauer spectrum. Ab initio calculations suggest that tunneling is interrupted effectively thanks to the exchange doublets. [ABSTRACT FROM AUTHOR]