Nickel-catalyzed, silyl-directed, ortho-borylation of arenes via an unusual Ni(II)/Ni(IV) catalytic cycle.

Nickel-catalyzed C-H bond functionalization reactions provide an impressive alternative to those with noble metal catalysts due to their unique reactivity and low cost. However, the regioselective C(sp2)-H borylation reaction of arenes accomplished by nickel catalyst remains limited. We herein disclose a silyl-directed ortho C(sp2)-H borylation of substituted arenes with a Ni(cod)2/PMe3/KHMDS catalyst system. Using readily available starting materials, this protocol provides easy access to ortho-borylated benzylic hydrosilanes bearing flexible substitution patterns. These products can serve as versatile building blocks for the synthesis of sila or sila/borine heterocycles under mild conditions. Control experiments and DFT calculations suggest that a catalytic amount of base prompts the formation of Ni(II)-Bpin-ate complex, likely related to the C(sp2)-H bond activation. This borylation reaction might follow an unusual Ni(II)/Ni(IV) catalytic cycle.

Enhanced wave absorption due to local flexibility on wide beams using mass-spring-damper scatterersa).

It is known that total absorption of flexural waves in a thin beam is possible through the use of monopole-dipole scatterers. In this study, we introduce a pair of identical monopole scatterers for near-total absorption of flexural waves in a thin and wide beam. Despite the two scatterers being both of the monopole type, the resonant modes of the scatterer pair exhibit monopole and dipole properties. By selecting the proper width for the beam, the two resonant modes degenerate, which leads to the total absorption. Although the beam is considerably wide, the frequency range of interest remains below the cut-on frequency of the n = 1 propagating mode, ensuring one-dimensional flexural wave propagation. Further simulations and theoretical analysis revealed that the degeneracy of the monopole and dipole modes results from their interaction with a higher-order localized flexural mode. The simulation results demonstrate absorption exceeding 99%, complemented by experimental data showing approximately 90% absorption.

Extreme material parameters accessible by active acoustic metamaterials with Willis coupling.

Active acoustic metamaterials incorporate electric circuit elements that input energy into an otherwise passive medium to aptly modulate the effective material properties. Here, we propose an active acoustic metamaterial with Willis coupling to drastically extend the tunability of the effective density and bulk modulus with the accessible parameter range enlarged by at least two orders of magnitude compared to that of a non-Willis metamaterial. Traditional active metamaterial designs are based on local resonances without considering the Willis coupling that limit their accessible effective material parameter range. Our design adopts a unit cell structure with two sensor-transducer pairs coupling the acoustic response on both sides of the metamaterial by detecting incident waves and driving active signals asymmetrically superimposed onto the passive response of the material. The Willis coupling results from feedback control circuits with unequal gains. These asymmetric feedback control circuits use Willis coupling to expand the accessible range of the effective density and bulk modulus of the metamaterial. The extreme effective material parameters realizable by the metamaterials will remarkably broaden their applications in biomedical imaging, noise control, and transformation acoustics-based cloaking.

Design and characterization of a three-dimensional anisotropic additively manufactured pentamode material.

A metamaterial of particular interest for underwater applications is the three-dimensional (3D) anisotropic pentamode (PM), i.e., a structure designed to support a single longitudinal wave with a sound speed that depends on the propagation direction. The present work attempts to experimentally verify anisotropic sound speeds predicted by finite element simulations using additively manufactured anisotropic 3D PM samples made of titanium. The samples were suspended in front of a plane wave source emitting a broadband chirp in a water tank to measure time of flight for wavefronts with and without the PM present. The measurement utilizes a deconvolution method that extracts the band limited impulse response of data gathered by a scanning hydrophone in a plane of constant depth behind the samples. Supporting material takes the form of finite element simulations developed to model the response of a semi-infinite PM medium to an incident normal plane wave. A technique to extract the longitudinal PM wave speed for frequency domain simulations based on Fourier series expansions is given.

Borane-catalyzed selective dihydrosilylation of terminal alkynes: reaction development and mechanistic insight.

Here, we describe simple B(C6F5)3-catalyzed mono- and dihydrosilylation reactions of terminal alkynes by using a silane-tuned chemoselectivity strategy, affording vinylsilanes and unsymmetrical geminal bis(silanes). This strategy is applicable to the dihydrosilylation of both aliphatic and aryl terminal alkynes with different silane combinations. Gram-scale synthesis and conducting the reaction without the exclusion of air and moisture demonstrate the practicality of this methodology. The synthetic utility of the resulting products was further highlighted by the structural diversification of geminal bis(silanes) through transforming the secondary silane into other silyl groups. Comprehensive theoretical calculations combined with kinetical isotope labeling studies have shown that a prominent kinetic differentiation between the hydrosilylation of alkynes and vinylsilane is responsible for the chemoselective construction of unsymmetrical 1,1-bis(silanes).

Fano-Like Acoustic Resonance for Subwavelength Directional Sensing: 0-360 Degree Measurement.

Directional sound sensing plays a critical role in many applications involving the localization of a sound source. However, the sensing range limit and fabrication difficulties of current acoustic sensing technologies pose challenges in realizing compact subwavelength direction sensors. Here, a subwavelength directional sensor is demonstrated, which can detect the angle of an incident wave in a full angle range (0°âˆ¼360°). The directional sensing is realized with acoustic coupling of Helmholtz resonators each supporting a monopolar resonance, which are monitored by conventional microphones. When these resonators scatter sound into free-space acoustic modes, the scattered waves from each resonator interfere, resulting in a Fano-like resonance where the spectral responses of the constituent resonators are drastically different from each other. This work provides a critical understanding of resonant coupling as well as a viable solution for directional sensing.

Selective Formation of S4- and T-Symmetric Supramolecular Tetrahedral Cages and Helicates in Polar Media Assembled via Cooperative Action of Coordination and Hydrogen Bonds.

We report on the synthesis and self-assembly study of novel supramolecular monomers encompassing quadruple hydrogen-bonding motifs and metal-coordinating 2,2'-bipyridine units. When mixed with metal ions such as Fe2+ or Zn2+, the tetrahedron cage complexes are formed in quantitative yields and full diastereoselectivity, even in highly polar acetonitrile or methanol solvents. The symmetry of the complexes obtained has been shown to depend critically on the flexibility of the ligand. Restriction of the rotation of the hydrogen-bonding unit with respect to the metal-coordinating site results in a T-symmetric cage, whereas introducing flexibility either through a methylene linker or rotating benzene ring allows the formation of S4-symmetric cages with self-filled interior. In addition, the possibility to select between tetrahedral cages or helicates and to control the dimensions of the aggregate has been demonstrated with a three-component assembly using external hydrogen-bonding molecular inserts or by varying the radius of the metal ion (Hg2+ vs Fe2+). Self-sorting studies of individual Fe2+ complexes with ligands of different sizes revealed their inertness toward ligand scrambling.

Broadband focusing of underwater sound using a transparent pentamode lens.

An inhomogeneous acoustic metamaterial lens based on spatial variation of refractive index for broadband focusing of underwater sound is reported. The index gradient follows a modified hyperbolic secant profile designed to reduce aberration and suppress side lobes. The gradient index (GRIN) lens is comprised of transversely isotropic hexagonal microstructures with tunable quasi-static bulk modulus and mass density. In addition, the unit cells are impedance-matched to water and have in-plane shear modulus negligible compared to the effective bulk modulus. The flat GRIN lens is fabricated by cutting hexagonal centimeter scale hollow microstructures in aluminum plates, which are then stacked and sealed from the exterior water. Broadband focusing effects are observed within the homogenization regime of the lattice in both finite element simulations and underwater measurements (20-40 kHz). This design approach has potential applications in medical ultrasound imaging and underwater acoustic communications.

Focusing, refraction, and asymmetric transmission of elastic waves in solid metamaterials with aligned parallel gaps.

Gradient index (GRIN), refractive, and asymmetric transmission devices for elastic waves are designed using a solid with aligned parallel gaps. The gaps are assumed to be thin so that they can be considered as parallel cracks separating elastic plate waveguides. The plates do not interact with one another directly, only at their ends where they connect to the exterior solid. To formulate the transmission and reflection coefficients for SV- and P-waves, an analytical model is established using thin plate theory that couples the waveguide modes with the waves in the exterior body. The GRIN lens is designed by varying the thickness of the plates to achieve different flexural wave speeds. The refractive effect of SV-waves is achieved by designing the slope of the edge of the plate array, and keeping the ratio between plate length and flexural wavelength fixed. The asymmetric transmission of P-waves is achieved by sending an incident P-wave at a critical angle, at which total conversion to SV-wave occurs. An array of parallel gaps perpendicular to the propagation direction of the reflected waves stop the SV-wave but let P-waves travel through. Examples of focusing, steering, and asymmetric transmission devices are discussed.