Na2Ga7: A Zintl-Wade Phase Related to "α-Tetragonal Boron".

Na2Ga7 crystallizes with the orthorhombic space group Pnma (no. 62; a = 14.8580(6) Å, b = 8.6766(6) Å, and c = 11.6105(5) Å; Z = 8) and constitutes a filled variant of the Li2B12Si2 structure type. The crystal structure consists of a network of icosahedral Ga12 units with 12 exohedral bonds and four-bonded Ga atoms in which the Na atoms occupy the channels and cavities. The atomic arrangement is consistent with the Zintl [(4b)Ga]- and Wade [(12b)Ga12]2- electron counting approach. The compound forms peritectically from Na7Ga13 and the melt at 501 °C and does not show a homogeneity range. The band structure calculations predict semiconducting behavior consistent with the electron balance [Na+]4[(Ga12)2-][Ga-]2. Magnetic susceptibility measurements show that Na2Ga7 is diamagnetic.

A Multiply Bonded Trigonal-Planar Bismuth(III) Complex: Prodigious Lewis Acidity, Solvatochromism, Etherification, and Semiconducting Characteristics.

The formation of a hitherto unknown 4-center, 6π-conjugated trigonal-planar complex, [Bi{Cr(CO)5 }3 ]- (1), is reported, in which the oxidation state of the Bi atom is +3, as evidenced by XAS, XPS, and DFT calculations. The BiIII atom in 1 has dual donor and acceptor properties in its bonding mode. In contrast to the mild Lewis acidity of BiIII , the central Bi in 1 functions as a prodigious Lewis acid site to exhibit strong affinity toward F- ions, unique solvatochromic properties, intriguing etherification through the C-O bond cleavage of alcohols, and surprising semiconducting characteristics with an ultra-narrow optical band gap of 1.02 eV, which can be attributed to the intermolecular Bi⋅⋅⋅O and O⋅⋅⋅O interactions in the solid state. The tetrahedral Fe(CO)4 -adduct [{Fe(CO)4 }Bi{Cr(CO)5 }3 ]3- (1-Fe) allowed the selective demetallation to afford the isoelectronic multiply bonded BiCr3 -complex 1 and the BiCr2 Fe-complex, [Bi{Cr(CO)5 }2 {Fe(CO)4 }]- (2), which may open a novel pathway for the design of the heterometal-incorporated trigonal-planar Bi-Cr complexes.

Semiconducting Coordination Polymers Based on the Predesigned Ternary Te-Fe-Cu Carbonyl Cluster and Conjugation-Interrupted Dipyridyl Linkers.

A series of semiconducting cluster-incorporated Cu-based coordination polymers, namely, 1D zigzag polymers [{TeFe3 (CO)9 Cu2 }(L)]n (L=1,2-bis(4-pyridyl)ethane (bpea), 1; L=1,2-bis(4-pyridyl)ethylene (bpee), 5), 2D honeycomb-like polymers [{TeFe3 (CO)9 Cu}Cu(L)2.5 ]n (L=bpea, 2; L=bpee, 6), and 2D wave-like cation-anion polymer [{Cu2 (L)4 }({TeFe3 (CO)9 Cu}2 (L))]n (L=1,3-bis(4-pyridyl)propane (bpp), 4), as well as the macrocycle [{TeFe3 (CO)9 Cu2 }2 (bpp)2 ] (3) have been quantitatively synthesized via the liquid-assisted grinding from the pre-designed cluster [TeFe3 (CO)9 Cu2 (MeCN)2 ] with conjugated or conjugation-interrupted dipyridyl linkers. Notably, the most conjugation-interrupted bpp-bridged polymer 4 exhibited extraordinary semiconducting characteristics with an ultra-narrow bandgap of 1.43 eV and a DC conductivity of 1.5×10-2 Ω-1  cm-1 , which violates our knowledge, mainly attributed to the through-space electron transport via non-classical C-H⋅⋅⋅O(carbonyl) hydrogen bonds and aromatic C-H⋅⋅⋅π interactions. The incorporated Te-Fe-CO anions can not only provide numerous possibilities for secondary interactions within these Cu-based polymers but also serve as a redox-active coordination ligand to promote their conductivities. The intriguing structure-property relationships were studied by X-ray and DFT analyses and further demonstrated by significant change in the oxidation state of Cu atoms by XPS and Cu K-edge XANES.

Ordering by cation replacement in the system Na2-xLixGa7.

Samples of the pseudo-binary system Na2-xLixGa7 (x ≤ 1) were synthesized from the elements at 300 °C in sealed Ta ampoules or by the reaction of Na2Ga7 with LiCl. The peritectic formation temperature decreases with increasing Li content from 501(2) °C (x = 0) to 489(2) °C (x = 1). The boundary compositions Na2Ga7 and Na1Li1Ga7 crystallize with different structure types related by a group-subgroup relation. While the Na-rich compositions (x ≤ 0.5) represent a substitutional solid solution (space group Pnma), the Li-rich compositions feature an unconventional replacement mechanism in which Li atoms occupying interstitial positions induce vancancies at the Na positions (space group Cmce). The crystal structure of Na1Li1Ga7 (a = 8.562(1) Å, b = 14.822(2) Å, c = 11.454(2) Å; Z = 8) was determined from X-ray single-crystal diffraction data, and reveals an anionic framework comprising 12-bonded Ga12 icosahedra and 4-bonded Ga atoms, with alkali-metal atoms occupying channels and cavities. The arrangement of cations makes NaLiGa7 a new structure type within the MgB12Si2 structure family. Band structure calculations for the composition NaLiGa7 predict semiconducting behavior consistent with the balance [Na+]2[Li+]2[(Ga12)2-][Ga-]2, considering closo Wade clusters [(12b)Ga12]2- and Zintl anions [(4b)Ga]-. Susceptibility measurements indicate temperature-independent diamagnetic behavior.

Fabrication of an artificial nanosucker device with a large area nanotube array of metallic glass.

The concurrent attachment and detachment movements of geckos on virtually any type of surface via their foot pads have inspired us to develop a thermal device with numerous arrangements of a multi-layer thin film together with electrodes that can help modify the temperature of the surface via application of a voltage. A sequential fabrication process was employed on a large-scale integration to generate well-defined contact hole arrays of photoresist for use as templates on the electrode-based device. The photoresist templates were then subjected to sputter deposition of the metallic glass Zr55Cu30Al10Ni5. Consequently, a metallic glass nanotube (MGNT) array having a nominal wall thickness of 100 nm was obtained after removal of the photoresist template. When a water droplet was placed on the MGNT array, close nanochambers of metallic glass were formed. By applying voltage, the surface was heated to increase the pressure inside the nanochambers; this generated an expanding force that raised the droplet; thus, the static water contact angle (SWCA) was increased. In contrast, a sucking force was generated during surface cooling, which decreased the SWCA. Our fabrication strategy exploits the MGNT array surface as nanosuckers, which can mimic the climbing aptitude of geckos as they attach to (>10 N m-2) and detach from (0.26 N m-2) surfaces at 0.5 and 3 V of applied voltage, respectively. Thus, the climbing aptitude of geckos can be mimicked by employing the processing strategy presented herein for the development of artificial foot pads.

Thin-film metallic glass: an effective diffusion barrier for Se-doped AgSbTe2 thermoelectric modules.

The thermal stability of joints in thermoelectric (TE) modules, which are degraded during interdiffusion between the TE material and the contacting metal, needs to be addressed in order to utilize TE technology for competitive, sustainable energy applications. Herein, we deposit a 200 nm-thick Zr-based thin-film metallic glass (TFMG), which acts as an effective diffusion barrier layer with low electrical contact resistivity, on a high-zT Se-doped AgSbTe2 substrate. The reaction couples structured with TFMG/TE are annealed at 673 K for 8-360 hours and analyzed by electron microscopy. No observable IMCs (intermetallic compounds) are formed at the TFMG/TE interface, suggesting the effective inhibition of atomic diffusion that may be attributed to the grain-boundary-free structure of TFMG. The minor amount of Se acts as a tracer species, and a homogeneous Se-rich region is found nearing the TFMG/TE interface, which guarantees satisfactory bonding at the joint. The diffusion of Se, which has the smallest atomic volume of all the elements from the TE substrate, is found to follow Fick's second law. The calculated diffusivity (D) of Se in TFMG falls in the range of D~10-20-10-23(m2/s), which is 106~107 and 1012~1013 times smaller than those of Ni [10-14-10-17(m2/s)] and Cu [10-8-10-11(m2/s)] in Bi2Te3, respectively.

Non-stick syringe needles: Beneficial effects of thin film metallic glass coating.

This paper reports on the use of Zr-based (Zr53Cu33Al9Ta5) thin film metallic glass (TFMG) for the coating of syringe needles and compares the results with those obtained using titanium nitride and pure titanium coatings. TFMG coatings were shown to reduce insertion forces by ∼66% and retraction forces by ∼72%, when tested using polyurethane rubber block. The benefits of TFMG-coated needles were also observed when tested using muscle tissue from pigs. In nano-scratch tests, the TFMG coatings achieved a coefficient of friction (COF) of just ∼0.05, which is about one order of magnitude lower than those of other coatings. Finite-element modeling also indicates a significant reduction in injection and retraction forces. The COF can be attributed to the absence of grain boundaries in the TFMG coating as well as a smooth surface morphology and low surface free energy.

Nitric oxide reduces Cu toxicity and Cu-induced NH4+ accumulation in rice leaves.

Nitric oxide (NO) is a highly reactive, membrane-permeable free radical, which has recently emerged as an important antioxidant. Here we investigated the protective effect of NO against the toxicity and NH4+ accumulation in rice leaves caused by excess CuSO4 (10mmol L(-1)). It was found that free radical scavengers (sodium benzoate, thiourea, and reduced glutathione) reduced the toxicity and NH4+ accumulation in rice leaves caused by excess CuSO4. NO donor sodium nitroprusside (SNP) was also effective in reducing CuSO4-induced toxicity and NH4+ accumulation in rice leaves. The protective effect of SNP on the toxicity and NH4+ accumulation can be reversed by 2-(4-carboxy-2-phenyl)-4,4,5,5-tetramethyl- imidazoline-1-oxyl-3-oxide, a NO scavenger, suggesting that the protective effect of SNP is attributable to NO released. Results obtained in the present study suggest that reduction of CuSO4-induced toxicity and NH4+ accumulation by SNP is most likely mediated through its ability to scavenge active oxygen species.

Iron carbonyl cluster-incorporated Cu(I) NHC complexes in homocoupling of arylboronic acids: an effective [TeFe3(CO)9](2-) ligand.

A new type of TeFe3(CO)9-incorporated dicopper NHC complex was obtained directly from one-pot reactions. By the introduction of the cluster anion [TeFe3(CO)9](2-) and NHCs as the ligands, these di-Cu(i)-based complexes exhibited pronounced catalytic activities toward the homocoupling of arylboronic acids with low Cu loadings and high yields (up to 98%).