Photoluminescence of Seven-Coordinate Zirconium and Hafnium Complexes with 2,2′-Pyridylpyrrolide Ligands

Luminescent seven-coordinated zirconium and hafnium complexes bearing three mono-anionic 2,2′-pyridylpyrrolide ligands and one chloride were synthesized. Solid-state structures and the dynamic behaviors in solution were probed by X-ray crystallography and variable temperature ¹H NMR experiments, respectively. Absorption spectroscopy and time-dependent density functional theory (TD-DFT) calculations supported a hybrid of ligand-to-metal charge transfer (LMCT)/ligand-to-ligand charge transfer (LLCT) for the visible light absorption band. The complexes (^MePMP^Me)₃MCl (M=Zr, Hf, ^MePMP^Me=3,5-dimethyl-2-(2-pyridyl)pyrrolide) are emissive in solution at room temperature upon irradiation with visible light due to a combination of phosphorescence and fluorescence characterized by excited state lifetimes in the μs and low to sub-ns timescale, respectively. Electrochemical experiments revealed that the zirconium complex possesses a reversible redox event under highly reducing condition (−2.29 V vs. Fc^+/0).     

Analyses of reaction rate data for the simple hydrolysis of acetic anhydride in the acetonitrile/water and acetone/water cosolvent systems using recently developed thermodynamic rate equations

This article presents reaction rate data for the simple hydrolysis of acetic anhydride in the acetonitrile/water and acetone/water cosolvent systems and regression analyses using recently developed thermodynamic rate equations that contain electrostatic and solvent-solute terms. The isomole fraction plots for these reaction systems are linear, and previous theoretical work has shown that the electrostatic term is negligible for such systems. On the other hand, the reaction rates are dependent upon the cosolvent mole fraction, indicating that the solvent-solute term, which is modeled empirically, is significant. The results of the analyses provide the foundation for a paradigm shift away from the emphasis on electrostatic effects to more tenable explanations of kinetic behavior in solvent systems.     

Inductive tools for connected delta-matroids and multimatroids

We prove a splitter theorem for tight multimatroids, generalizing the corresponding result for matroids, obtained independently by Brylawski and Seymour. Further corollaries give splitter theorems for delta-matroids and ribbon graphs.     

A Study of Tate Homology via the Approximation Theory with Applications to the Depth Formula

Acta Mathematica Sinica, English Series - In this paper we are concerned with absolute, relative and Tate Tor modules. In the first part of the paper we generalize a result of Avramov and...     

Asymptotic models for a long,elastic cylinder

We study asymptotic expansions for the displacement field of a long elastic cylinder under various constitutive assumptions. We show that under simple hypotheses it is possible to derive from the equations of continuum mechanics two known beam equations and several different string models. Some of the string models correspond to those studied by S. Antman and R. Dickey. We also show that under our assumptions the problem of asymptotic expansion can be reduced to that of algebraic geometry.Research partially supported by NSF Grant DMR-8612369.     

Experimental investigation of creep-crack-tip deformation using moiré interferometry

High-temperature moiré interferometry was applied to obtain full-field creep-crack-tip displacements of a three-point bend Al 2024-T4 specimen uner constant temperature of 200°C up to 720 hr.C ^* was evaluated by the moiré data obtained at discrete time intervals. Test results indicate that under steady-state creep condition, the creepcrack-tipv-displacement rate agrees with the asymptotic solution based on theC ^* integral. However, no creeping behavior was observed for the crack-tipu-displacement field aftert=276 hr. This discrepancy may be due to the initial large creep-crack-tip blunting and cavitation damage which alter the creep-crack-tip singular field such that theC ^* integral is no longer applicable to characterize the steady-state creep-crack-tip field. Postmortem studies of the tested specimen also revealed transgranular fracture path with the ordered grain boundaries perpendicular to the crack line, which may relate to the existence of the substantial crack-tip blunting and noncreeping behavior of theu-displacement field, i.e., the size and shape of material grain boundaries play an important role in the crack-tip-creeping behavior of the material.Paper was preseted at the 1991 SEM Spring Conference on Experimental Mechanics held in Milwaukee, WI on June 9–13.