Catalyst- and solvent-free regiospecific SNHAr phosphinylation of pyridines with H-phosphinates mediated by benzoylphenylacetylene.

Pyridines undergo a facile SNHAr phosphinylation with H-phosphinates under catalyst- and solvent-free conditions (50-55 °C) in the presence of benzoylphenylacetylene to afford 4-phosphinylpyridines in up to 68% yield. In this reaction, benzoylphenylacetylene activates the pyridine ring by the formation of a 1,3(4)-dipolar complex, deprotonates H-phosphinates to generate P-centered anions and finally acts as an oxidizer, being eliminated from an intermediate ion pair. Terminal electron-deficient acetylenes (methyl propiolate and benzoylacetylene) are inefficient as mediators in the above SNHAr process.

Quantum Bipolaron Superconductivity from Quadratic Electron-Phonon Coupling.

When the electron-phonon coupling is quadratic in the phonon coordinates, electrons can pair to form bipolarons due to phonon zero-point fluctuations, a purely quantum effect. We study superconductivity originating from this pairing mechanism in a minimal model and reveal that, in the strong coupling regime, the critical temperature (T_{c}) is only mildly suppressed by the coupling strength, in stark contrast to the exponential suppression in linearly coupled systems, thus implying higher optimal T_{c} values. We demonstrate that large coupling constants of this flavor are achieved in known materials such as perovskites, and discuss strategies to realize such superconductivity using superlattices.

Time-reversal symmetry breaking superconductivity between twisted cuprate superconductors.

Twisted interfaces between stacked van der Waals (vdW) cuprate crystals present a platform for engineering superconducting order parameters by adjusting stacking angles. Using a cryogenic assembly technique, we construct twisted vdW Josephson junctions (JJs) at atomically sharp interfaces between Bi2Sr2CaCu2O8+x crystals, with quality approaching the limit set by intrinsic JJs. Near 45° twist angle, we observe fractional Shapiro steps and Fraunhofer patterns, consistent with the existence of two degenerate Josephson ground states related by time-reversal symmetry (TRS). By programming the JJ current bias sequence, we controllably break TRS to place the JJ into either of the two ground states, realizing reversible Josephson diodes without external magnetic fields. Our results open a path to engineering topological devices at higher temperatures.

Dihydropyrrole-3-thiones: one-pot synthesis from propargylamines, acyl chlorides and sodium sulfide.

An efficient one-pot synthesis of 1,2,5-trisubstituted-1,2-dihydro-3H-pyrrole-3-thiones (up to 91% yield), representatives of essentially new heterocyclic systems, by the successive treatment of available propargylamines with acyl chlorides (PdCl2/CuI/Ph3P/Et3N, toluene, 40-45 °C, 3 h) and sodium sulfide (Na2S·9H2O, EtOH, 20-25 °C, 7 h) has been developed. The synthesis comprises the addition of sulfide anions to the formed aminoacetylenic ketones followed by dehydrative cyclization of the prototropically rearranged adducts.

Dielectric Relaxation by Quantum Critical Magnons.

We report the experimental observation of dielectric relaxation by quantum critical magnons. Complex capacitance measurements reveal a dissipative feature with a temperature-dependent amplitude due to low-energy lattice excitations and an activation behavior of the relaxation time. The activation energy softens close to a field-tuned magnetic quantum critical point at H=H_{c} and follows single-magnon energy for H>H_{c}, showing its magnetic origin. Our study demonstrates the electrical activity of coupled low-energy spin and lattice excitations, an example of quantum multiferroic behavior.

Current- and Field-Induced Topology in Twisted Nodal Superconductors.

We show that interlayer current induces topological superconductivity in twisted bilayers of nodal superconductors. A bulk gap opens and achieves its maximum near a "magic" twist angle θ_{MA}. Chiral edge modes lead to a quantized thermal Hall effect at low temperatures. Furthermore, we show that an in-plane magnetic field creates a periodic lattice of topological domains with edge modes forming low-energy bands. We predict their signatures in scanning tunneling microscopy. Estimates for candidate materials indicate that twist angles θ∼θ_{MA} are optimal for observing the predicted effects.

Superconductivity from energy fluctuations in dilute quantum critical polar metals.

Superconductivity in low carrier density metals challenges the conventional electron-phonon theory due to the absence of retardation required to overcome Coulomb repulsion. Here we demonstrate that pairing mediated by energy fluctuations, ubiquitously present close to continuous phase transitions, occurs in dilute quantum critical polar metals and results in a dome-like dependence of the superconducting Tc on carrier density, characteristic of non-BCS superconductors. In quantum critical polar metals, the Coulomb repulsion is heavily screened, while the critical transverse optical phonons decouple from the electron charge. In the resulting vacuum, long-range attractive interactions emerge from the energy fluctuations of the critical phonons, resembling the gravitational interactions of a chargeless dark matter universe. Our estimates show that this mechanism may explain the critical temperatures observed in doped SrTiO3. We provide predictions for the enhancement of superconductivity near polar quantum criticality in two- and three-dimensional materials that can be used to test our theory.

Electron-Deficient Acetylenes as Three-Modal Adjuvants in SNH Reaction of Pyridinoids with Phosphorus Nucleophiles.

Publications covering a new easy metal-free functionalization of pyridinoids (pyridines, quinolines, isoquinolines, acridine) under the action of the system of electron-deficient acetylenes (acetylenecarboxylic acid esters, acylacetylenes)/P-nucleophiles (phosphine chalcogenides, H-phosphonates) are reviewed. Special attention is focused on a SNH reaction of the regioselective cross-coupling of pyridines with secondary phosphine chalcogenides triggered by acylacetylenes to give 4-chalcogenophosphorylpyridines. In these processes, acetylenes act as three-modal adjuvants (i) activating the pyridine ring towards P-nucleophiles, (ii) deprotonating the P-H bond and (iii) facilitating the nucleophilic addition of the P-centered anion to a heterocyclic moiety followed by the release of the selectively reduced acetylenes (E-alkenes).

Oxidative cross-coupling of secondary phosphine chalcogenides with amino alcohols and aminophenols: aspects of the reaction chemoselectivity.

Secondary phosphine chalcogenides react with primary amino alcohols under mild conditions (room temperature, molar ratio of the initial reagents 1 : 1) in a CCl4/Et3N oxidizing system to chemoselectively deliver amides of chalcogenophosphinic acids with free OH groups. Under similar conditions, mono-cross-coupling between secondary phosphine chalcogenides and 1,2- or 1,3-aminophenols proceeds only with the participation of phenolic hydroxyl to give aminophenylchalcogenophosphinic O-esters. The yields of the synthesized functional amides or esters are 60-85%.

Magnon Bose-Einstein condensation and superconductivity in a frustrated Kondo lattice.

Motivated by recent experiments on magnetically frustrated heavy fermion metals, we theoretically study the phase diagram of the Kondo lattice model with a nonmagnetic valence bond solid ground state on a ladder. A similar physical setting may be naturally occurring in [Formula: see text], [Formula: see text], and [Formula: see text] compounds. In the insulating limit, the application of a magnetic field drives a quantum phase transition to an easy-plane antiferromagnet, which is described by a Bose-Einstein condensation of magnons. Using a combination of field theoretical techniques and density matrix renormalization group calculations we demonstrate that in one dimension this transition is stable in the presence of a metallic Fermi sea, and its universality class in the local magnetic response is unaffected by the itinerant gapless fermions. Moreover, we find that fluctuations about the valence bond solid ground state can mediate an attractive interaction that drives unconventional superconducting correlations. We discuss the extensions of our findings to higher dimensions and argue that depending on the filling of conduction electrons, the magnon Bose-Einstein condensation transition can remain stable in a metal also in dimensions two and three.

Multiband Quantum Criticality of Polar Metals.

Motivated by recent experimental realizations of polar metals with broken inversion symmetry, we explore the emergence of strong correlations driven by criticality when the polar transition temperature is tuned to zero. Overcoming previously discussed challenges, we demonstrate a robust mechanism for coupling between the critical mode and electrons in multiband metals. We identify and characterize several novel interacting phases, including non-Fermi liquids, when band crossings are close to the Fermi level and present their experimental signatures for three generic types of band crossings.

Catalyst-Free Double CH-Functionalization of Quinolines with Phosphine Oxides via Two SNHAr Reaction Sequences.

Quinolines undergo catalyst-free double CH-functionalization upon treatment with secondary phosphine oxides (70-75 °C, 20-48 h) followed by oxidation of the intermediate 2,4-bisphosphoryltetrahydroquinolines with chloranil. The yields of the target 2,4-bisphosphorylated quinolines are up to 77%. Thus, a double-SNHAr reaction sequence in the same molecule of quinoline has been realized. In the case of 2,4-bisphenylphosphoryltetrahydroquinolines, the aromatization occurs with elimination of one molecule of diphenylphosphine oxide to afford the products of monofunctionalization, 4-diphenylphosphorylquinolines, in 40-45% yields.

Acetylene-Triggered Reductive Incorporation of Phosphine Chalcogenides into a Quinoline Scaffold: Toward SNHAr Reaction.

Quinolines react with acylacetylenes and secondary phosphine chalcogenides at 20-75 °C to afford N-acylvinyl-2(1)-chalcogenophosphoryldihydroquinolines in good and excellent yields. Unlike the pyridine-derived similar intermediates, which eliminate E-alkenes to give aromatic chalcogenophosphorylpyridines, thereby completing SNHAr reaction, with quinolines, the reaction stops at the formation of the above phosphorylated N-acylvinyl-dihydroquinolines, thus representing a pendant SNHAr process. This reaction opens a one-pot atom-economic single-step access to pharmaceutically targeted phosphorylated functionalized dihydroquinolines and isoquinolines.

Dynamic gas extraction of iodine in combination with a silver triangular nanoplate-modified paper strip for colorimetric determination of iodine and of iodine-interacting compounds.

A method is described for sensitive and selective detection of iodine by using a paper strip modified with silver triangular nanoplates (AgTNPs). It is based on the extraction of iodine from a solution into a flow of air via dynamic gas extraction and transferring it through a reactive paper modified with AgTNPs. The interaction of AgTNPs with iodine results in a color change from blue to white. This can be visually detected and monitored by digital colorimetry. The dynamic gas extraction is highly selective for volatile compounds so that a sample pretreatment is minimal. Due to the sensitivity of AgTNPs for iodine, the limit of its detection is as low as 7 µg L-1, and the analytical range is of 20-200 µg L-1. The method also was applied in a new approach for determination of organic compounds that can interact with iodine. The organic compound is exposed to an excess of iodine, and this is followed by detection of residual iodine as described above. The method was applied to the determination of ascorbic acid, caffeine and the drug metamizole. Graphical abstract Schematic representation of a procedure of organic iodine-interacting compounds (Org.) determination. It is based on their iodination followed by gas extraction of the residual iodine, its interaction with silver triangular nanoplates and colorimetric detection with a scanner.

Catalyst-Free Phosphorylation of Acridine with Secondary Phosphine Chalcogenides: Nucleophilic Addition vs SNHAr Reaction.

Acridine adds secondary phosphine chalcogenides HP(X)R2 (X = O, S, Se; R = Ar, ArAlk) under catalyst-free conditions at 70-75 °C (both in the presence and absence of the electron-deficient acetylenes) to give 9-chalcogenophosphoryl-9,10-dihydroacridines in 61-94% yields. This contrasts with pyridines, which under similar conditions undergo an SNHAr reaction, wherein electron-deficient acetylenes play the role of oxidants. For acridine, the SNHAr step has been accomplished by the oxidation of the intermediate 9-phosphoryl-9,10-dihydroacridines (X = O) with chloranil.

Metal-free site selective cross-coupling of pyridines with secondary phosphine chalcogenides using acylacetylenes as oxidants.

Pyridines undergo site selective cross-coupling with secondary phosphine chalcogenides (oxides, sulfides, and selenides) in the presence of acylphenylacetylenes under metal-free mild conditions (70-75 °C, MeCN) to afford 4-chalcogenophosphoryl pyridines in up to 71% yield. In this new type of SNHAr reaction acylacetylenes act as oxidants, being stereoselectively reduced to the corresponding olefins of the E-configuration.

Towards highly selective detection using metal nanoparticles: A case of silver triangular nanoplates and chlorine.

The article describes a novel approach towards improving selectivity of volatile compounds detection using metal nanoparticles. It is based on combination of sensitive optical detection using convenient nanoparticle-modified paper test strips and dynamic gas extraction improving selectivity to volatile compounds. A simple and inexpensive setup allowing for realization of this combination is described. Analytical prospects of the approach are shown by the example of chlorine determination in highly salted aqueous solutions using silver triangular nanoplates and digital colorimetry. The limit of detection is equal to 0.03mgL-1 and the determination range is 0.1-2mgL-1. This determination can be successfully carried out in solutions containing at least 2·105 greater molar amounts of Na+, K+, Zn2+, Cl-, SO42-, and H2PO4- with no sample pretreatment. The approach seems to be compatible with different types of nanoparticles with respect to detection of various analytes, thus having good opportunities for further development.

Towards the development of solid-state platform optical sensors: aggregation of gold nanoparticles on polyurethane foam.

In this paper, we report on a novel type of nanocomposites based on gold nanoparticles (AuNPs) and polyurethane foam (PUF), which represents an ability of AuNP aggregation on solid polymer matrix with the strongly different selectivity in comparison with aggregation of the same AuNPs in solution. This may indicate that a new type of aggregation takes place, which can be called solid-phase aggregation. A systematic study using diffuse reflectance spectroscopy revealed features of the solid-phase aggregation. The PUF-AuNPs nanocomposites can be synthesized by a simple and low cost procedure based on adsorption of different type AuNPs from aqueous solution onto PUF. Prospects of obtained composite materials for sensing some organic compounds using diffuse reflectance spectroscopy or colorimetry are shown. This nanocomposites have the increased selectivity to thiols allowing for their determination with limits of detection of 0.01-0.05µgmL-1 and relative standard deviations of 3-5%. Charged species that affect AuNPs in solution do not influence them on PUF.