On the first excited state of137Ba

The first excited state of¹³⁷Ba has been excited by the inelastic scattering of accelerator-produced neutrons. The energy of this state at 283.5 keV is not in agreement with the generally accepted value of 279.2 keV, but is in accord with other recent measurements. No evidence for a doublet of states near this energy is found.     

Acyl and α-Ketoacyl Complexes of Pt(II) with Weak Donor Ligands

Treatment of trans-Pt(COCOPh)(Cl)(PPh₃)₂ (1a) with AgBF₄in THF led to the formation of a metastatic complex trans-[Pt(COCOPh)(THF)(PPh₃)₂](BF₄) (2) which readily underwent ligand substitution to give a cationic aqua complex trans-[Pt(COCOPh)(OH₂)(PPh₃)₂](BF₄) (5a). Complex 5a has been characterized spectroscopically and crystallographically. Analogous reaction of trans-Pt(COCOOMe)(Cl)(PPh₃)₂ (1b) with Ag(CF₃SO₃) in dried CH₂C1₂ was found first to yield a methoxyoxalyl triflato complextrans-Pt(COCOOMe)(OTf)(PPh₃)₂ (6). Attempts to crystallize the triflato product in CH₂-cl₂hexane under ambient conditions also afforded an aqua complex of the triflate salt f/wu-[Pt(COCOOMe)(OH₂)(PPhj)₂](CF₃SO₃) (5b). Complex 5a in a noncoordinating solvent such as CH₂C1₂ or CHCl₃ suffered spontaneous decarbonylation to form first cis-[Pt(COPh)(CO)(PPh₃)₂l(BF₄) (3a) then the thermodynamically stable isomer trans-[Pt(COPh)(CO)(PPh₃)₂](BF₄) (3b). Crystallization of complex 3b under ambient conditions resulted in an aqua benzoyl complex trans-[Pt(COPh)(OH₂)(PPh₃)₂](BF₄) (7). The replacement of the H_2O ligand in complex 7 by CO was done simply by bubbling CO into the solution of 7. The single crystal structures of 5b and 7 have been determined by X-ray diffraction. The distances of the Pt-O bonds in 5a, 5b, and 7 support that the aqua ligand is a weak donor in such cationic aquaorganoplatinum(lI) complexes, in agreement with their lability to the substitution reactions.     

Dual room-temperature fluorescent and phosphorescent emission in 8-quinolinolate osmium(II) carbonyl complexes: rationalization and generalization of intersystem crossing dynamics

A new series of quinolinolate osmium carbonyl complexes were synthesized and characterized by spectroscopic methods. Single-crystal X-ray diffraction studies indicate that these complexes consist of an octahedral ligand arrangement with one chelating quinolinolate, one tfa or halide ligand, and three mutually orthogonal terminal CO ligands. Variation of the substituents on quinolinolate ligands imposes obvious electronic or structural effects, while changing the tfa ligand to an electron-donating iodide slightly increases the charge density on the central osmium atom. These Os(II) complexes show salient dual emissions consisting of fluorescence and phosphorescence, the spectral properties and relaxation dynamics of which have been studied comprehensively. The results, in combination with the theoretical approaches, lead us to propose that the emission mainly originates from the quinolinolate pi pi* state. Both experimental and theoretical approaches generalize various types of intersystem crossing versus those of the tris(quinolinolate) iridium Ir(Q)3, and their relative efficiencies were accessed on the basis of the associated frontier orbital configurations. Our results suggest that [1d(pi)pi* absolute value(H(so))3 pi pi*] (or [3d(pi)pi* absolute value(H(so))1 pi pi*]) in combination with a smaller deltaE(S1-T1) gap (i.e., increasing the MLCT (d(pi)pi*) character) is the main driving force to induce the ultrafast S1 --> T1 intersystem crossing in the third-row transition metal complexes, giving the strong phosphorescent emission.     

Self-assembly of tetrahedral and trigonal antiprismatic clusters [Fe4(L4)4] and [Fe6(L5)6] on the basis of trigonal tris-bidentate chelators

In a one-pot reaction, the tetranuclear iron chelate complex [Fe4(L4)4] 6 was generated from benzene-1,3,5-tricarboxylic acid trichloride (4), bis-tert-butyl malonate (5a), methyllithium, and iron(II) dichloride under aerobic conditions. Alternatively, hexanuclear iron chelate complex [Fe(L5)6] 7 was formed starting from bis-para-tolyl malonate (5b) by employing identical reaction conditions to those applied for the synthesis of 6. The clusters 6 and 7 are present as racemic mixtures of homoconfigurational (delta,delta,delta,delta)/(lambda,lambda,lambda,lambda)-fac or (delta,delta,delta,delta,delta,delta)/(lambda,lambda,lambda,lambda,lambda,lambda)-fac stereoisomers. The structures of 6 and 7 were unequivocally resolved by single-crystal X-ray analyses. The all-iron(III) character of 6 and 7 was determined by M?ssbauer spectroscopy.     

The fluorobasicities of ReF7 and IF7 as measured by the enthalpy change ΔH°(EF7(g) → EF6+(g) + F−(g))

Iridium hexafluoride oxidizes ReF₆ (via an ReF₆⁺ salt) and at room temperatures IrF₆, ReF₆, ReF₇ and (IrF₅)₄ are each present in the equilibrium mixture. From these and related findings: ΔH°(ReF₆ → ReF₆⁺ + e^?) 1092 ± 27 kj mole^?1(261 ± 6 kcal mole^?1), and thermodynamic data are selected to yield ΔH°(ReF_7(g) → ReF₆⁺_(g) + F^?_(g))=893 ± 33 kj mole^?1(213 ± 8 kcal mole^?1). From observations on the stability of IF₆⁺BF₄^? and the lattice enthalpy evaluation for the salt, ΔH°(IF_7(g) → IF₆⁺_(g) + F^?_(g))= 870 ± 24 kj mole^?1(208 ± 6 kcal mole^?1).     

Optimizing Multi-stage Production for an Assembly-Type Supply Chain with Unequal Sized Batch Shipments

This paper studies the multi-stage logistics and inventory problem in an?assembly-type supply chain where a uniform lot size is produced uninterruptedly with a single setup at each stage. Partial lots, or sub-batches, can be transported to next stage upon completion. Unequal sub-batch sizes at each stage follow geometric series and the numbers of sub-batches across stages are allowed to be different. Since the mainline and each branch line of an assembly-type supply chain are series-type supply chains, a model of the series-type supply chain is first established and a model of the assembly-type supply chain is subsequently developed. Optimization algorithms that determine the economic lot sizes, the optimal sub-batch sizes and the number of sub-batches for each stage are developed. The polynomial-time algorithms incorporate the optimality properties derived in the paper to find the lower and upper bounds of the solutions by constructing the solution ranges and then the optimal solutions accordingly.     

DRDF analysis of wide-angle x-ray scattering of natural rubber

A differential radial distribution function (DRDF) of molten natural rubber (NR) was derived from its wide-angle x-ray scattering (WAXS) data. Three peaks with Bragg spacings 4.85, 2.31, and 1.23 Å corresponding, respectively, to interchain, C₁-C₃ and C₁ -C₂ distances are present in the corrected WAXS curve. The derived DRDF, which is shown to be greatly improved than the ones published so far, contains six peaks located at 1.51, 2.48, 3.98, 5.68, 10.65, and 15.25 Å. Maximum contributions of intramolecular atomic distances to the radial distribution peaks were estimated and compared with the experimental results. The comparison shows that the first three peaks are intramolecular in origin and the remaining peaks are predominantly due to intermolecular regularities. A periodicity of an approximately constant interval of 5.26 Å is found between the intermolecular peaks and is attributable to the organizations of more or less parallel chain segments in the material. This finding provided additional evidence for the presence of local lateral ordering to the extent of about 30 Å in molten-state natural rubber.     

A [001]-Oriented Hittorf's Phosphorus Nanorods/Polymeric Carbon Nitride Heterostructure for Boosting Wide-Spectrum-Responsive Photocatalytic Hydrogen Evolution from Pure Water

Red phosphorus is a promising photocatalyst with wide visible-light absorption up to 700 nm, but the fast charge recombination limits its photocatalytic hydrogen evolution reaction (HER) activity. Now, [001]-oriented Hittorf's phosphorus (HP) nanorods were successfully grown on polymeric carbon nitride (PCN) by a chemical vapor deposition strategy. Compared with the bare PCN and HP, the optimized PCN@HP hybrid exhibited a significantly enhanced photocatalytic activity, with HER rates reaching 33.2 and 17.5 μmol h⁻¹ from pure water under simulated solar light and visible light irradiation, respectively. It was theoretically and experimentally indicated that the strong electronic coupling between PCN and [001]-oriented HP nanorods gave rise to the enhanced visible light absorption and the greatly accelerated photoinduced electron–hole separation and transfer, which benefited the photocatalytic HER performance.     

Identifying a dot-matrix hologram with the fringe-overlapping phenomena of grating dots

Dot-matrix holograms created by two-beam writers contain many grating dots. Because the phase difference between two laser beams for interference cannot be controlled accurately, the fringe positions of grating dots are randomly determined. Therefore, fringe positions are a good kind of tool to identify dot-matrix holograms. In this paper, a number difference between two special fringes of a target grating dot is used to identify a dot-matrix hologram. The two special fringes are determined by three grating dots with parallel fringes. The first special fringe is corresponding to a fringe pair with the best matching for the fringes of the target grating dot and the fringes of the second grating dot. The second special fringe is corresponding to a fringe pair with the best matching for the fringes of the target grating dot and the fringes of the third grating dot. An experiment has proved the proposed method practical and feasible. Because reproducing a grating dot with a specified fringe number difference is difficult, the proposed method is excellent for anti-counterfeiting.