Understanding Pt•••Pt and Pt•••Au metallophilic interactions in single salt and double salt complexes using photophysical tools

Seven [Pt(tpy)X]Y (X=Cl, Y=Cl•2H2O, X=Cl, Y=Cl•DMSO, X=Cl, Y=PF6, X=Cl, Y=SbF6, X=Cl, Y=SbF6•CH3CN, X=Br, Y= Br•2H2O, and X=Br, Y=PF6) complexes were prepared and characterized. Structural analysis shows consistent patterns in Pt^...Pt interactions that vary slightly depending on the coordinating halogen, X, counteranion, Y, and lattice solvent. Diffuse reflectance was used to identify solid-state ^1MMLCT absorption bands, and the relationship between Pt-Pt distance and ^1MMLCT absorption energy will be discussed. Metallophilic Pt^...Au interactions in [Pt(tpy)X][AuX'2] (X=X'=CN, X=Cl, X'=C6F5, X=Br, X'=C6F5, X=I, X'=C6F5) double salts were investigated. Structural characterization showed Pt^...Au metallophilic interactions were only observed in X=X'=CN, while Pt^...Pt interactions were observed in X=I, X'=C6F5. The closest contacts in X=Cl, X'=C6F5 and X=Br, X'=C6F5 were between the Lewis acidic Pt center of the cation and a Lewis basic ortho carbon of the pentafluorophenyl group on the anion. Photophysical characterization showed MMLCT features in the solid-state but only monomeric MLCT features localized on the [Pt]+ and [Au]- units in solution. The chromophore [Pt(tpy)(CCPh)]^+ was studied in [Pt][Au(C6F5)2] and [Pt][Pt(C^N)(CN)2] (C^N = ppy, F2ppy, or bzq) double salts. Structural characterization showed formation of a channel of [Pt(tpy)(CCPh)]+ moieties supported by metallophilic interactions in [Pt][Au(C6F5)2] and [Pt][Pt(F2ppy)(CN)2]. Solution electronic absorption spectra showed MLCT features centered on the cation and anion units for all four complexes. An additional ^1MMLCT band near 520 nm is present in the solid-state arising from Pt^...Pt interactions formed between cation units. Three [Pt(tpy)Cl][Pt(C^N)(CN)2] (C^N = ppy, F2ppy, and bzq) double salts were prepared and characterized. A new solution MMLCT feature was identified for all three double salts using UV-vis and fluorescence spectroscopy. Support of solution cation and anion association using solution conductivity and dynamic light scattering measurements will be discussed

The History of the American Lutheran Foreign Missions in Asia, Africa, and Oceania since World War I

The primary purpose of this thesis is to give a brief history of each mission field, but in some cases where we believe that material on the topography of the land, the climatic conditions, the religious conceptions of the heathen natives, etc. are not generally available - such topics are included

Folly of Sky, Earth, Man: The Work of Yatsuka Hajime

Japanese names are revealing; choice of script may suggest a word as indigenous or not, and render a Japanese concept more foreign or visa-versa. Many architects, although Yatsuka is not among them, fabricate words, relying on the meaning of Japanese characters

Katsura Imperial Villa: A Brief Descriptive Bibliography, with Illustrations

There are three imperial residences in Kyoto: Gosho (京都御所), rebuilt in 1855 and used for formal affairs even today; Shūgakuin (修学院離宮), a summer retreat on mountain slopes built in the mid-seventeenth century; and Katsura Imperial Retreat (桂離宮), slightly older than Shūgakuin. Upon the death of the Hachijō imperial line in 1881, Katsura came into the hands of the reigning household; shortly afterward, the Imperial Household Ministry was formed and took responsibility for the care of such sites. Sometimes grouped with the other residences, Nijō Palace was originally built not for the imperial household but for the warriors who effectively ruled Japan from the seventeenth to the middle of the nineteenth century; today, it too is managed by the Imperial Household Agency (the scope and name of the Imperial Household Ministry having changed at the end of World War II). Of these four, Katsura, with its extensive grounds and esteemed teahouses in addition to a large, shoin-style residence, is best known of all, used both at home and abroad to illustrate arguments about architecture and national tradition. Yet even so, much remains to be said about the complex, as demonstrated by this brief descriptive bibliography. Download High-Resolution PD

INVESTIGATION OF THE ACCURACY OF FINITE ELEMENT MODEL PREDICTIONS OF INTRINSIC RESIDUAL STRESS IN 3D WOVEN COMPOSITES BY COMPARING THE MODEL PREDICTIONS OF SURFACE DISPLACEMENTS FROM HOLE DRILLING TO EXPERIMENTAL MEASUREMENTS

The goal of this effort was to determine how accurately finite element models of 3D woven composites constructed using Dynamic Fabric Mechanics Analyzer predict the intrinsic residual stress field that results from cooling going from the curing temperature to room temperature. Hole drilling methods were used to estimate and measure the local stresses at selected locations in 3D woven composites. Blind holes were virtually drilled in one orthogonal and multiple ply-to-ply models and the resulting in-plane surface displacement fields were compared to the surface displacement fields measured using electronic speckle pattern interferometry. The shape of the experimental and predicted displacement fields were similar in both the orthogonal and ply-to-ply structures, except along the orthogonal warp tow, where the fields were opposite. The magnitude of the measured displacement fields was approximately 1/5th that of the predicted value both parallel and perpendicular to the tows in the orthogonal structure, except along the orthogonal warp tow, which was -1/5th. This is attributed to microcracking below the warp tow relieving the residual stress. The magnitude of the experimental displacements was between 1/3rd to two times larger than the prediction transverse to the tow axis in the ply-to-ply structure. Along the warp tow axis, on one side the experimental result matches the prediction while on the other side the experimental displacement was two times larger. Along the weft tow in the ply-to-ply the experimental displacement matched the predicted displacement. The effect of drill depth on surface displacement was studied by drilling holes in 0.5mm depth increments and comparing experimental results to finite element models of an orthogonal and a 12x10 picks per inch ply-to-ply structure. The experimental displacements match the predicted displacements in shape and magnitude. The model does a good job of predicting the effect of drill depth on surface displacement. The effect of pick spacing and volume fraction on surface displacements from hole drilling was studied for composites with a ply-to-ply weave with 12x12 (warp/weft) picks per inch (ppi), 10x12 ppi, and 10x8 ppi. The finite element models used in this section contained a resin overburden on top of the tows, affecting the accuracy of the predicted displacements. The experimental displacement fields were a good qualitative match to the predictions. The experimental transverse displacements were approximately 1/4 of the predicted displacements. The model increasingly under predicts the displacement along the tow axis as the number of picks-per-inch decreases