Highly active bifunctional diporphyrin and triporphyrin catalysts were synthesized through Stille coupling reactions. As compared with a porphyrin monomer, both exhibited improved catalytic activities for the reaction of CO2 with epoxides to form cyclic carbonates, because of the multiple catalytic sites which cooperatively activate the epoxide. Catalytic activities were carefully investigated by controlling temperature, reaction time, and catalyst loading, and very high turnover number and turnover frequency were obtained: 220 000 and 46 000 h(-1) , respectively, for the magnesium catalyst, and 310 000 and 40 000 h(-1) , respectively, for the zinc catalyst. Results obtained with a zinc/free-base hybrid diporphyrin catalyst demonstrated that the Br(-) ions on the adjacent porphyrin moiety also function as nucleophiles.

The emergence of the nematic electronic state that breaks rotational symmetry is one of the most fascinating properties of the iron-based superconductors, and has relevance to cuprates as well. FeSe has a unique ground state in which superconductivity coexists with a nematic order without long-range magnetic ordering, providing a significant opportunity to investigate the role of nematicity in the superconducting pairing interaction. Here, to reveal how the superconducting gap evolves with nematicity, we measure the thermal conductivity and specific heat of FeSe S , in which the nematicity is suppressed by isoelectronic sulfur substitution and a nematic critical point (NCP) appears at [Formula: see text] We find that, in the whole nematic regime ([Formula: see text]), the field dependence of two quantities consistently shows two-gap behavior; one gap is small but highly anisotropic with deep minima or line nodes, and the other is larger and more isotropic. In stark contrast, in the tetragonal regime ([Formula: see text]), the larger gap becomes strongly anisotropic, demonstrating an abrupt change in the superconducting gap structure at the NCP. Near the NCP, charge fluctuations of [Formula: see text] and [Formula: see text] orbitals are enhanced equally in the tetragonal side, whereas they develop differently in the orthorhombic side. Our observation therefore directly implies that the orbital-dependent nature of the nematic fluctuations has a strong impact on the superconducting gap structure and hence on the pairing interaction.

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Quantum oscillations (QOs) in transport and thermodynamic parameters at high magnetic fields are an unambiguous signature of the Fermi surface, the defining characteristic of a metal. Therefore, recent observations of QOs in insulating SmB 6 [1-4] and YbB 12 , in particular the QOs of the resistivity ρ xx in YbB 12 [5], have been a big surprise, pointing to the formation of a novel state of quantum matter. Despite the large charge gap inferred from the insulating behaviour of ρ xx , these compounds seemingly host a Fermi surface at high magnetic fields. However, the nature of the ground state in zero field has been little explored. Here we report the use of low-temperature heat-transport measurements to discover gapless, itinerant, charge-neutral excitations in the ground state of YbB 12 . At zero field, despite ρ xx being far larger than that of conventional metals, a sizable linear temperature dependent term in the thermal conductivity is clearly resolved in the zero-temperature limit (κ xx /T (T → 0) = κ 0 xx /T = 0), analogous to normal metallic behaviour. Such a residual κ 0 xx /T term at zero field, which is absent in SmB 6 [3, 6, 7], leads to a spectacular violation of the Wiedemann-Franz law: the Lorenz ratio L = κ xx ρ xx /T is 10 4 -10 5 times larger than that expected in conventional metals. These data indicate that YbB 12 is a charge insulator but a thermal metal, suggesting the presence of itinerant neutral fermions. Remarkably, more insulating crystals with larger activation energies exhibit a larger amplitude of the resistive QOs as well as a larger κ 0 xx /T , in stark contrast to conventional metals. Moreover, we find that these fermions couple to magnetic field, despite their charge neutrality. Our findings expose novel gapless and highly itinerant, charge-neutral quasiparticles in this unconventional quantum state.In intermetallic 4f and 5f compounds, strong hybridization between itinerant and predominately localized electrons often opens an insulating gap [8,9]. Among

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A quantum spin liquid (QSL) is an exotic state of matter characterized by quantum entanglement and the absence of any broken symmetry. A long-standing open problem, which is a key for fundamental understanding the mysterious QSL states, is how the quantum fluctuations respond to randomness due to quenched disorder. Transition metal dichalcogenide 1T-TaS2 is a candidate material that hosts a QSL ground state with spin-1/2 on the two-dimensional perfect triangular lattice. Here, we performed systematic studies of low-temperature heat capacity and thermal conductivity on pure, Se-substituted and electron irradiated crystals of 1T-TaS2, where the substitution of S by Se induces weak disorder and electron irradiation induces strong quenched disorder. In pure 1T-TaS2, the linear temperature term of the heat capacity γT and the finite residual linear term of the thermal conductivity in the zero-temperature limit κ0/T ≡ κ/T (T → 0) are clearly resolved, consistent with the presence of gapless spinons with a Fermi surface. Moreover, while the strong magnetic field slightly enhances κ0/T , it strongly suppresses γ. These unusual contrasting responses to magnetic field imply the coexistence of two types of gapless excitations with itinerant and localized characters. Introduction of additional weak random exchange disorder in 1T-Ta(S1−xSex)2 leads to vanishing of κ0/T , indicating that the itinerant gapless excitations are sensitive to the disorder. On the other hand, in both pure and Se-substituted systems, the magnetic contribution of the heat capacity obeys a universal scaling relation, which is consistent with a theory that assumes the presence of localized orphan spins forming random singlets. These results appear to capture an essential feature of the QSL state of 1T-TaS2; localized orphan spins induced by disorder form random valence bonds and are surrounded by a QSL phase with spinon Fermi surface. Electron irradiation in pure 1T-TaS2 largely enhances γ and changes the scaling function dramatically, suggesting a possible new state of spin liquid.

A hydrogel was prepared by cross-linking poly(4-vinyl phenol) with ethylene glycol diglycidyl ether in order to examine the ion-specific swelling behavior. The swelling ratios to various kinds of aqueous salt solutions except for N(CH3)4Cl were almost constant, or the gels remained in a swollen state, up to their saturated concentrations. This unexpected result was ascribed to stabilization of hydrogen-bonding hydrations to the phenol OH proton and to the phenol ring (π electrons) by anions and cations, respectively. The supposed mechanism was supported by ab initio calculations for the corresponding small model systems.