Effects of substituents on bridging ligands on the single‐molecule magnet properties of Zn2Dy2 cluster complexes

Two new Zn₂Dy₂ complexes were constructed from Zn (II) salen‐type Schiff base complex fragment and 2,6‐pyridinedimethanol (H₂pdm) or its Br‐substituted analogue (4‐bromopyridine‐2,6‐diyl)dimethanol (H₂Brpdm); their molecular formulas are [Zn₂Dy₂(L)₂(pdm)₂(MeOH)₂](ClO₄)₂ [ 1 , H₂L = N, N′‐ bis(3‐methoxysalicylidene)‐1,3‐diaminopropane] and [Zn₂Dy₂(L)₂(Brpdm)₂(MeOH)₂](ClO₄)₂ [ 2 ], the Dy (III) ions of which have a NO₇ triangular dodecahedral coordination sphere. The two complexes show not only ferromagnetic interaction but also field‐induced single‐molecule magnet (SMM) behavior, which are rare Dy (III)‐containing cluster complexes with the NO₇ triangular dodecahedral coordination sphere that can show good magnetic relaxation. The energy barrier value of complex 2 is higher than those of complex 1 and the Dy (III) complexes with the DyNO₇ triangular dodecahedral coordination configuration reported in the literature.     

Dynamics of laser-induced cavitation bubble during expansion over sharp-edge geometry submerged in liquid – an inside view by diffuse illumination

Laser ablation in liquids is growing in popularity for various applications including nanoparticle production, breakdown spectroscopy, and surface functionalization. When laser pulse ablates the solid target submerged in liquid, a cavitation bubble develops. In case of “finite” geometries of ablated solids, liquid dynamical phenomena can occur inside the bubble when the bubble overflows the surface edge. To observe this dynamics, we use diffuse illumination of a flashlamp in combination with a high-speed videography by exposure times down to 250 ns. The developed theoretical modelling and its comparison with the experimental observations clearly prove that this approach widens the observable area inside the bubble. We thereby use it to study the dynamics of laser-induced cavitation bubble during its expansion over a sharp-edge (“cliff-like” 90°) geometry submerged in water, ethanol, and polyethylene glycol 300. The samples are 17 mm wide stainless steel plates with thickness in the range of 0.025–2 mm. Bubbles are induced on the samples by 1064-nm laser pulses with pulse durations of 7–60 ns and pulse energies of 10–55 mJ. We observe formation of a fixed-type secondary cavity behind the edge where low-pressure area develops due to bubble-driven flow of the liquid. This occurs when the velocity of liquid overflow exceeds ~20 m s⁻¹. A re-entrant liquid injection with up to ~40 m s⁻¹ velocity may occur inside the bubble when the bubble overflows the edge of the sample. Formation and characteristics of the jet evidently depend on the relation between the breakdown-edge offset and the bubble energy, as well as the properties of the surrounding liquid. Higher viscosity of the liquid prevents the generation of the jet.     

Characteristic behaviour of plasma fluctuations inside a plasma bubble in presence of a magnetic field due to the formation of a potential well

Experiments were carried out to observe the effect of a magnetic field and grid biasing voltage in presence of a plasma bubble in a magnetized, filamentary discharge plasma system. A spherical mesh grid of 80% optical transparency was negatively biased and introduced into the plasma for creating a plasma bubble. Diagnostics via an electrical Langmuir probe and a hot emissive probe were extensively used for scanning the plasma bubble. Plasma floating potential fluctuations were measured at three different positions of the plasma bubble. The instability in the pattern showed the dynamic transition from periodic to chaotic for increasing magnetic fields. Time scale analysis using continuous wavelet transform was carried out to identify the presence of non‐linearity from the contour plots. The mechanisms of the low‐frequency instabilities along with the transition to chaos could be qualitatively explained. Non‐linear techniques such as fast Fourier transform, phase space plot, and recurrence plot were used to explore the dynamics of the system appearing during plasma fluctuations. In order to demonstrate the observed chaotic phenomena in this study, characteristics of chaos such as the Lyapunov exponent were obtained from experimental time series data. The experimentally observed potential structure is confirmed with numerical analysis based on fluid hydrodynamics.     

When Gold Cations Meet Polyoxometalates

Merging gold(I) cations with polyoxometalate anions results in various interclusters and complexes. Herein, the synthesis of these newly emerging gold(I)/polyoxometalate materials is reviewed. The applications of these promising hybrids in organic catalysis are also summarized and evaluated in terms of the advantages and limitations of the catalysts including efficiency, synergistic effects and recyclability.     

New Perspectives for Old Clusters: Anderson–Evans Anions as Building Blocks of Large Polyoxometalate Frameworks in a Series of Heterometallic 3 d–4 f Species

A series of nine [Sb₇W₃₆O₁₃₃Ln₃M₂(OAc)(H₂O)₈]^17? heterometallic anions ( Ln₃M₂ ; Ln=La–Gd, M=Co; Ln=Ce, M=Ni and Zn) have been obtained by reacting 3 d metal disubstituted Krebs‐type tungstoantimonates(III) with early lanthanides. Their unique tetrameric structure contains a novel {MW₉O₃₃} capping unit formed by a planar {MW₆O₂₄} fragment to which three {WO₂} groups are condensed to form a tungstate skeleton identical to that of a hypothetical trilacunary derivative of the ?‐Keggin cluster. It is shown, for the first time, that classical Anderson–Evans {MW₆O₂₄} anions can act as building blocks to construct purely inorganic large frameworks. Unprecedented reactivity in the outer ring of these disk‐shaped species is also revealed. The Ln₃M₂ anions possess chirality owing to a {Sb₄O₄} cluster being encapsulated in left‐ or right‐handed orientations. Their ability to self‐associate in blackberry‐type vesicles in solution has been assessed for the Ce₃Co₂ derivative.     

The Key Role of U28 in the Aqueous Self‐Assembly of Uranyl Peroxide Nanocages

For 11 years now, the structural diversity and aesthetic beauty of uranyl–peroxide capsules have fascinated researchers from the diverse fields of mineralogy, polyoxometalate chemistry, and nuclear fuel technologies. There is still much to be learned about the mechanisms of the self‐assembly process, and the role of solution parameters including pH, alkali template, temperature, time, and others. Here we have exploited the high solubility of the UO₂²⁺/H₂O₂/LiOH aqueous system to address the effect of the hydroxide concentration. Important techniques of this study are single‐crystal X‐ray diffraction, small‐angle X‐ray scattering, and Raman spectroscopy. Three key phases dominate the solution speciation as a function of time and the LiOH/UO₂²⁺ ratio: the uranyl–triperoxide monomer [UO₂(O₂)₃]^4?and the two capsules [(UO₂)(O₂)(OH)]₂₄^24?(U₂₄) and [(UO₂)(O₂)_1.5]₂₈^28?(U₂₈). When the LiOH/U ratio is around three, U₂₈ forms rapidly and this cluster can be isolated in high yield and purity. This result was most surprising and challenges the hypothesis that alkali templating is the most important determinant in the cluster geometry. Moreover, analogous experiments with KOH, NH₄OH, and TEAOH (TEA=tetraethylammonium) also rapidly yield U₂₈, which suggests that U₂₈ is the kinetically favored species. Complete mapping of the pH–time phase space reveals only a narrow window of the U₂₈ dominance, which is why it was previously overlooked as an important kinetic species in this chemical system, as well as others with different counterions.     

Thermal Conversion of Methane to Formaldehyde Promoted by Gold in AuNbO3+ Cluster Cations

In addition to generation of a methyl radical, formation of a formaldehyde molecule was observed in the thermal reaction of methane with AuNbO₃⁺ heteronuclear oxide cluster cations. The clusters were prepared by laser ablation and mass‐selected to react with CH₄ in an ion‐trap reactor under thermal collision conditions. The reaction was studied by mass spectrometry and DFT calculations. The latter indicated that the gold atom promotes formaldehyde formation through transformation of an Au?O bond into an Au?Nb bond during the reaction.     

Is it True That the Normal Valence‐Length Correlation Is Irrelevant for Metal–Metal Bonds?

The most intriguing feature of metal–metal bonds in inorganic compounds is an apparent lack of correlation between the bond order and the bond length. In this study, we combine a variety of literature data obtained by quantum chemistry and our results based on the empirical bond valence model (BVM), to confirm for the first time the existence of a normal exponential correlation between the effective bond order (EBO) and the length of the metal–metal bonds. The difference between the EBO and the formal bond order is attributed to steric conflict between the (TM)_n cluster (TM=transition metal) and its environment. This conflict, affected mainly by structural type, should cause high lattice strains, but electron redistribution around TM atoms, evident from the BVM calculations, results in a full or partial strain relaxation.