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  1. Organic trisradicals featuring three-fold symmetry have attracted significant interest because of their unique magnetic properties associated with spin frustration. Herein, we describe the synthesis and characterization of a triangular prism-shaped organic cage for which we have coined the name PrismCage6+ and its trisradical trication—TR3(•+). PrismCage6+ is composed of three 4,4'-bipyridinium dications and two 1,3,5-phenylene units bridged by six methylene groups. In the solid state, PrismCage6+ adopts a highly twisted conformation with close to C3 symmetry as a result of encapsulating one PF6− anion as a guest. PrismCage6+ undergoes stepwise reduction to its mono-, di- and trisradical cations in MeCN on account of strong electronic communication between its 4,4'-bipyridinium units. TR3(•+), which is obtained by reduction of PrismCage6+ employing CoCp2, adopts a triangular prism-shaped conformation with close to C2v symmetry in the solid state. Temperature-dependent continuous-wave and nutation frequency-selective EPR spectra of TR3(•+) in frozen N,N-dimethylformamide indicate its doublet ground state. The doublet-quartet energy gap of TR3(•+) is estimated to be −0.06 kcal mol−1 and the critical temperature of spin-state conversion is found to be ca. 50 K, suggesting that it displays pronounced spin-frustration at the molecular level. To the best of our knowledge, this example is the first organic radical cage to exhibit spin frustration. The trisradical trication of PrismCage6+ opens up new possibilities for fundamental investigations and potential applications in the fields of both organic cages and spin chemistry. 
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    Free, publicly-accessible full text available June 1, 2024
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  3. Abstract With the motivation to study how non-magnetic ion site disorder affects the quantum magnetism of Ba 3 CoSb 2 O 9 , a spin-1/2 equilateral triangular lattice antiferromagnet, we performed DC and AC susceptibility, specific heat, elastic and inelastic neutron scattering measurements on single crystalline samples of Ba 2.87 Sr 0.13 CoSb 2 O 9 with Sr doping on non-magnetic Ba 2+ ion sites. The results show that Ba 2.87 Sr 0.13 CoSb 2 O 9 exhibits (i) a two-step magnetic transition at 2.7 K and 3.3 K, respectively; (ii) a possible canted 120 degree spin structure at zero field with reduced ordered moment as 1.24 μ B /Co; (iii) a series of spin state transitions for both H ∥ ab -plane and H ∥ c -axis. For H ∥ ab -plane, the magnetization plateau feature related to the up–up–down phase is significantly suppressed; (iv) an inelastic neutron scattering spectrum with only one gapped mode at zero field, which splits to one gapless and one gapped mode at 9 T. All these features are distinctly different from those observed for the parent compound Ba 3 CoSb 2 O 9 , which demonstrates that the non-magnetic ion site disorder (the Sr doping) plays a complex role on the magnetic properties beyond the conventionally expected randomization of the exchange interactions. We propose the additional effects including the enhancement of quantum spin fluctuations and introduction of a possible spatial anisotropy through the local structural distortions. 
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  4. Abstract The magnetic ground state of the pyrochlore Yb 2 GaSbO 7 has not been established. The persistent spin fluctuations observed by muon spin-relaxation measurements at low temperatures have not been adequately explained for this material using existing theories for quantum magnetism. Here we report on the synthesis and characterisation of Yb 2 GaSbO 7 to revisit the nature of the magnetic ground state. Through DC and AC magnetic susceptibility, heat capacity, and neutron scattering experiments, we observe evidence for a dynamical ground state that makes Yb 2 GaSbO 7 a promising candidate for disorder-induced spin-liquid or spin-singlet behaviour. This state is quite fragile, being tuned to a splayed ferromagnet in a modest magnetic field μ 0 H c  ~ 1.5 T. 
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  5. Abstract

    Spin-fluctuation-mediated unconventional superconductivity can emerge at the border of magnetism, featuring a superconducting order parameter that changes sign in momentum space. Detection of such a sign-change is experimentally challenging, since most probes are not phase-sensitive. The observation of a spin resonance mode (SRM) from inelastic neutron scattering is often seen as strong phase-sensitive evidence for a sign-changing superconducting order parameter, by assuming the SRM is a spin-excitonic bound state. Here we show that for the heavy fermion superconductor CeCoIn5, its SRM defies expectations for a spin-excitonic bound state, and is not a manifestation of sign-changing superconductivity. Instead, the SRM in CeCoIn5likely arises from a reduction of damping to a magnon-like mode in the superconducting state, due to its proximity to magnetic quantum criticality. Our findings emphasize the need for more stringent tests of whether SRMs are spin-excitonic, when using their presence to evidence sign-changing superconductivity.

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