The presence of a quantum-critical point (QCP) can significantly affect the thermodynamic properties of a material at finite temperatures T . This is reflected, e.g., in the entropy landscape SðT,rÞ in the vicinity of a QCP, yielding particularly strong variations for varying the tuning parameter r such as pressure or magnetic field B. Here we report on the determination of the critical enhancement of ∂S∕∂B near a B-induced QCP via absolute measurements of the magnetocaloric effect (MCE), ð∂T ∕∂BÞ S and demonstrate that the accumulation of entropy around the QCP can be used for efficient low-temperature magnetic cooling. Our proof of principle is based on measurements and theoretical calculations of the MCE and the cooling performance for a Cu 2þ -containing coordination polymer, which is a very good realization of a spin-½ antiferromagnetic Heisenberg chain-one of the simplest quantum-critical systems.quantum criticality | quantum magnetism | low-dimensional spin systems | magnetothermal effect T he magnetocaloric effect (MCE), i.e., a temperature change in response to an adiabatic change of the magnetic field, has been widely used for refrigeration. Although up until now applications have focused on cryogenic temperatures (1-3), possible extensions to room temperature have been discussed (4). The MCE is an intrinsic property of all magnetic materials in which the entropy S changes with magnetic field B. Paramagnetic salts have been the materials of choice for low-temperature refrigeration (1), including space applications (5-7), with an area of operation ranging from about one or two degrees Kelvin down to some hundredths or even thousandths degree Kelvin. Owing to their large ΔS∕ΔB values, the ease of operation, and the applicability under microgravity conditions, paramagnets have matured to a valuable alternative to 3 He-4 He dilution refrigerators, the standard cooling technology for reaching sub-Kelvin temperatures.A large MCE also characterizes a distinctly different class of materials, where the low-temperature properties are governed by pronounced quantum many-body effects. These materials exhibit a B-induced quantum-critical point (QCP)-a zero-temperature phase transition-and the MCE has been used to study their quantum criticality (8)(9)(10)(11)(12)(13)(14) or to determine their B-T phase diagrams (15)(16)(17)(18)(19). The aim of the present work is to provide an accurate determination of the enhanced MCE upon approaching a B-induced QCP both as a function of B and T and to explore the potential of this effect for magnetic cooling.Materials in the vicinity of a QCP have been of particular current interest, as their properties reflect critical behavior arising from quantum fluctuations instead of thermal fluctuations that govern classical critical points (20). Prominent examples of findings made here include the intriguing low-temperature behaviors encountered in some heavy-fermion metals, itinerant transition metal magnets (21 and references cited therein, 22), or magnetic insulators (23, 24) and the ...

Four highly soluble square-planar Cu(II) and Ni(II) complexes of siloxy-salens (2SiCu, 2SiNi) and hydroxy-salens (2Cu, 2Ni) have been synthesized. An X-ray crystal structure analysis was performed on 2SiCu, 2SiNi, and 2Ni. The compounds have been investigated by cyclic voltammetry, UV-vis-NIR spectroelectrochemistry, and EPR spectroscopy. According to these results, the monooxidized species [2SiCu]+ and [2SiNi]+ are to be classified as Robin-Day class II and III systems, respectively. Magnetic measurements on the dinuclear (PMDTA)Cu(II) complex 1Cu2 x (PF6)2 with deprotonated 1,4-dihydroxy-2,5-bis(pyrazol-1-yl)-benzene (1) linker revealed antiferromagnetic coupling between the two Cu(II) ions thereby resulting in an isolated dimer compound. Coordination polymers [1Cu]n(H2O)(2n) of Cu(II) ions and bridging p-hydroquinone linkers were obtained from CuSO4 x 5 H2O and 1,4-dihydroxy-2,5-bis(pyrazol-1-yl)benzene. X-ray crystallography revealed linear chains running along the crystallographic a-direction and stacked along the b-axis. Within these chains, the Cu(II) ions are coordinated by two pyrazolyl nitrogen atoms and two p-hydroquinone oxygen atoms in a square-planar fashion.

Two-dimensional (2D) systems with continuous symmetry lack conventional long-range order because of thermal fluctuations. Instead, as pointed out by Berezinskii, Kosterlitz and Thouless (BKT), 2D systems may exhibit so-called topological order driven by the binding of vortex-antivortex pairs. Signatures of the BKT mechanism have been observed in thin films, specially designed heterostructures, layered magnets and trapped atomic gases. Here we report on an alternative approach for studying BKT physics by using a chemically constructed multilayer magnet. The novelty of this approach is to use molecular-based pairs of spin S ¼ ½ ions, which, by the application of a magnetic field, provide a gas of magnetic excitations. On the basis of measurements of the magnetic susceptibility and specific heat on a so-designed material, combined with density functional theory and quantum Monte Carlo calculations, we conclude that these excitations have a distinct 2D character, consistent with a BKT scenario, implying the emergence of vortices and antivortices.

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We have synthesized and investigated a new biphenyl-4,4′bis(nitronyl nitroxide) radical with intermediately strong antiferromagnetic interactions. This organic biradical belongs to a family of materials that can be used as a building block for the design of new quantum magnets. For quantum magnetism, special attention has been paid to coupled S = 1 / 2 dimer compounds, which when placed in a magnetic field, can be used as model systems for interacting boson gases. Short contacts between the oxygen atoms of the nitronyl nitroxide units and the hydrogen atoms of the benzene rings stabilize a surprisingly planar geometry of the biphenyl spacer and are responsible for a small magnetic interdimer coupling. The strength of the antiferromagnetic intradimer coupling constant J/k B = −14.0 ± 0.9 K, fitting the experimental SQUID-data using an isolated-dimer model. The deviations from the isolated-dimer model are attributed to a small interdimer coupling J′/k B , on the order of 1 K, consistent with the crystal structure.