Giant magnetic-field dependence of the coupling between spin Tomonaga-Luttinger liquids in BaCo2V2O8

We use nuclear magnetic resonance to map the complete low-temperature phase diagram of the antiferromagnetic Ising-like spin-chain system BaCo2V2O8 as a function of the magnetic field applied along the chains. In contrast to the predicted crossover from the longitudinal incommensurate phase to the transverse antiferromagnetic phase, we find a sequence of three magnetically ordered phases between the critical fields 3.8 T and 22.8 T. Their origin is traced to the giant magnetic-field dependence of the total effective coupling between spin chains, extracted to vary by a factor of 24. We explain this novel phenomenon as emerging from the combination of nontrivially coupled spin chains and incommensurate spin fluctuations in the chains treated as Tomonaga-Luttinger liquids.Comment: 6 pages, 3 figure

Supramolecular chemistry of helical foldamers at the solid-liquid interface: self-assembled monolayers and anion recognition

The synthesis of a redox-active helical foldamer and its immobilization onto a gold electrode are described. These large molecular architectures are grafted in a reproducible manner and provide foldamer-based self-assembled monolayers displaying recognition properties

Redox-controlled hybridization of helical foldamers

Tetrathiafulvalene redox units were grafted at both extremities of an oligopyridine–dicarboxamide foldamer through a straightforward copper-catalyzed azide–alkyne cycloaddition. The present work demonstrates that the hybridization equilibrium of foldamers can be tuned through redox stimulations

Vesignieite: An S=1/2 Kagome Antiferromagnet with Dominant Third-Neighbor Exchange

The spin- 1 2 kagome antiferromagnet is an archetypal frustrated system predicted to host a variety of exotic magnetic states. We show using neutron scattering measurements that deuterated vesignieite BaCu 3 V 2 O 8 ( OD ) 2 , a fully stoichiometric S = 1 / 2 kagome magnet with < 1 % lattice distortion, orders magnetically at T N = 9     K into a multi- k coplanar variant of the predicted triple- k octahedral structure. We find that this structure is stabilized by a dominant antiferromagnetic third-neighbor exchange J 3 with minor first- or second-neighbor exchanges. The spin-wave spectrum is well described by a J 3 -only model including a tiny symmetric exchange anisotropy

Evolution of field-induced metastable phases in the Shastry-Sutherland lattice magnet TmB4

The appearance of a plateau in the magnetization of a quantum spin system subject to continuously varying magnetic field invites the identification of a topological quantization. Indeed, the magnetization plateaus at 1/8 and 1/2 of saturation in TmB4 have been suggested to be intrinsic, resulting from such a topological quantization, or, alternatively, to be metastable phases. By means of neutron- and x-ray-scattering experiments and magnetization measurements, we show that the 1/8 plateau is metastable, arising because the spin dynamics are frozen below T ≈ 4.5 K. Our experiments show that in this part of the phase diagram of TmB4, many long-ranged orders with different propagation vectors may appear and coexist, particularly as the applied field drives the system from one plateau to another. The magnetic structures accommodating a magnetization of ≈1/8 seem to be particularly favorable, but still only appear if the system has sufficient dynamics to reorganize into a superstructure as it is driven toward the expected plateau. This work demonstrates that TmB4 represents a model material for the study of slow dynamics, in and out of equilibrium

Structural Conformers of (1,3-Dithiol-2-ylidene)ethanethioamides: The Balance Between Thioamide Rotation and Preservation of Classical Sulfur-Sulfur Hypervalent Bonds

The reaction of N-(2-phthalimidoethyl)-N-alkylisopropylamines and S2Cl2 gave 4-N-(2-phthalimidoethyl)-N-alkylamino-5-chloro-1,2-dithiol-3-thiones that quantitatively cycloadded to dimethyl or diethyl acetylenedicarboxylate to give stable thioacid chlorides, which in turn reacted with one equivalent of aniline or a thiole to give thioanilides or a dithioester. Several compounds of this series showed atropisomers that were studied by a combination of dynamic NMR, simulation of the signals, conformational analysis by DFT methods, and single crystal X-ray diffraction, showing a good correlation between the theoretical calculations, the experimental values of energies, and the preferred conformations in the solid state. The steric hindering of the crowded substitution at the central amine group was found to be the reason for the presence of permanent atropisomers in this series of compounds and the cause of a unique disposition of the thioxo group at close-to-right angles with respect to the plane defined by the 1,3-dithiole ring in the dithiafulvene derivatives, thus breaking the sulfur–sulfur hypervalent bond that is always found in this kind of compounds.Ministerio de Economıá y Competitividad, Spain (Project CTQ2012- 31611), Junta de Castilla y León, Consejería de Educación y Cultura y Fondo Social Europeo (Project BU246A12-1), and the European Commission, Seventh Framework Programme (Project SNIFFER FP7-SEC-2012-312411

Mechanical Bonds and Topological Effects in Radical Dimer Stabilization

While mechanical bonding stabilizes tetrathiafulvalene (TTF) radical dimers, the question arises: what role does topology play in catenanes containing TTF units? Here, we report how topology, together with mechanical bonding, in isomeric [3]- and doubly interlocked [2]catenanes controls the formation of TTF radical dimers within their structural frameworks, including a ring-in-ring complex (formed between an organoplatinum square and a {2+2} macrocyclic polyether containing two 1,5-dioxynaphthalene (DNP) and two TTF units) that is topologically isomeric with the doubly interlocked [2]catenane. The separate TTF units in the two {1+1} macrocycles (each containing also one DNP unit) of the isomeric [3]catenane exhibit slightly different redox properties compared with those in the {2+2} macrocycle present in the [2]catenane, while comparison with its topological isomer reveals substantially different redox behavior. Although the stabilities of the mixed-valence (TTF2)^(•+) dimers are similar in the two catenanes, the radical cationic (TTF^(•+))_2 dimer in the [2]catenane occurs only fleetingly compared with its prominent existence in the [3]catenane, while both dimers are absent altogether in the ring-in-ring complex. The electrochemical behavior of these three radically configurable isomers demonstrates that a fundamental relationship exists between topology and redox properties