Homo- and Heteronuclear Transition Metal Complexes Supported by Multinucleating Ligands

This dissertation is mainly divided into two sub-parts: organometallic and bioinorganic/materials projects. The approach for the projects involves the use of two different multinucleating ligands to synthesize mono- and multinuclear complexes. Chapter 2 describes the synthesis of a multinucleating tris(phosphinoaryl)benzene ligand used to support mono-nickel and palladium complexes. The isolated mononuclear complexes were observed to undergo intramolecular arene C¬–H to C–P functionalization. The transformation was studied by nuclear magnetic resonance spectroscopy and X-ray crystallography, and represents a rare type of C–H functionalization mechanism, facilitated by the interactions of the group 10 metal with the arene π–system.

Chapter 3 describes the construction of multinickel complexes supported by the same triphosphine ligand from Chapter 2. This chapter shows how the central arene in the ligand’s triarylbenzene framework can interact with dinickel and trinickel moieties in various binding modes. X-ray diffraction studies indicated that all compounds display strong metal–arene interactions. A cofacial triangulo nickel(0) complex supported by this ligand scaffold was also isolated and characterized. This chapter demonstrates the use of an arene as versatile ligand design element for small molecular clusters.

Chapter 4 presents the syntheses of a series of discrete mixed transition metal Mn oxido clusters and their characterization. The synthesis of these oxide clusters displaying two types of transition metals were targeted for systematic metal composition-property studies relevant to mixed transition metal oxides employed in electrocatalysis. A series of heterometallic trimanganese tetraoxido cubanes capped with a redox-active metal [MMn₃O₄] (M = Fe, Co, Ni, Cu) was synthesized starting from a [CaMn₃O₄] precursor and structurally characterized by X-ray crystallography and anomalous diffraction to conclusively determine that M is incorporated at a single position in the cluster. The electrochemical properties of these complexes were studied via cyclic voltammetry. The redox chemistry of the series of complexes was investigated by the addition of a reductant and oxidant. X-ray absorption and electron paramagnetic resonance spectroscopies were also employed to evaluate the product of the oxidation/reduction reaction to determine the site of electron transfer given the presence of two types of redox-active metals. Additional studies on oxygen atom transfer reactivities of [MMn₃O₄] and [MMn₃O₂] series were performed to investigate the effect of the heterometal M in the reaction rates.

Chapter 5 focuses on the use of [CoMn₃O₄] and [NiMn₃O₄] cubane complexes discussed in Chapter 4 as precursors to heterogeneous oxygen evolution reaction (OER) electrocatalysts. These well-defined complexes were dropcasted on electrodes with/without heat treatment, and the OER activities of the resulting films were evaluated. Multiple spectroscopic techniques were performed on the surface of the electrocatalysts to gain insight into the structure-function relationships based on the heterometallic composition. Depending on film preparation, the Co-Mn-oxide was found to change metal composition during catalysis, while the Ni-Mn oxide maintained the NiMn3 ratio. These studies represent the use of discrete heterometallic-oxide clusters as precursors for heterogeneous water oxidation catalysts.

Appendix A describes the ongoing effort to synthesize a series of heteromultimetallic [MMn₃X] clusters (X = O, S, F). Complexes such as [ZnMn₃O], [CoMn₃O], [Mn₃S], and [Mn₄F] have been synthesized and structurally characterized. An amino-bis-oxime ligand (PRABO) has been installed on the [ZnMn₃O] cluster. Upon the addition of O₂, the desymmetrized [ZnMn₃O] cluster only underwent an outer-sphere, one-electron oxidation. Efforts to build and manipulate other heterometallic [MMn₃X] clusters are still ongoing, targeting O₂ binding and reduction. Appendix B summarizes the multiple synthetic approaches to build a [Co₄O₄]-cubane complex relevant to heterogeneous OER electrocatalysis. Starting with the tricobalt cluster [LCo₃(O₂CR)₃] and treatment various strong oxidants that can serve as oxygen atom source in the presence Co²⁺ salt only yielded tricobalt mono–oxo complexes. Appendix C presents the efforts to model the H-cluster framework of [FeFe]-hydrogenase by incorporating a synthetic diiron complex onto a protein-supported or a synthetic ligand-supported [Fe₄S₄]-cluster. The mutant ferredoxin with a [Fe₄S₄]-cluster and triscarbene ligand have been characterized by multiple spectroscopic techniques. The reconstruction of an H-cluster mimic has not yet been achieved, due to the difficulty of obtaining crystallographic evidence and the ambiguity of the EPR results.

高精度微结构聚合物光栅的复制技术

光栅复制是降低光栅制造成本,提高产量的一条有效途径。研究了利用紫外压印技术复制微结构光栅的方法。使用玻璃基底矩形浮雕结构的微结构光栅作为母光栅,给出了利用聚二甲基硅氧烷(PDMS)制作光栅模具和在光敏聚合物材料上复制微结构光栅的详细过程。经过优化工艺条件,成功地复制了一系列不同周期和开口比的微结构光栅,测试了复制光栅和母光栅的衍射图像和0级与±1级的衍射强度,结果表明,复制光栅和母光栅的衍射图像与光强分布基本一致。

Coma measurement of projection optics in lithographic tools based on relative image displacements at multiple illumination settings

In this paper, we propose a novel method for measuring the coma aberrations of lithographic projection optics based on relative image displacements at multiple illumination settings. The measurement accuracy of coma can be improved because the phase-shifting gratings are more sensitive to the aberrations than the binary gratings used in the TAMIS technique, and the impact of distortion on displacements of aerial image can be eliminated when the relative image displacements are measured. The PROLITH simulation results show that, the measurement accuracy of coma increases by more than 25% under conventional illumination, and the measurement accuracy of primary coma increases by more than 20% under annular illumination, compared with the TAMIS technique. (c) 2007 Optical Society of America.

Design and control of an ultraprecision stage used in grating tiling

In petawatt laser system, the gratings used to compose pulse compressor are very large in size which can be only acquired currently by arraying small aperture gratings to form a large one instead, an approach referred to as grating tiling. Theory and experiments have demonstrated that the coherent addition of multiple small gratings to form a larger grating is viable, the key technology of which is to control the relative position and orientation of each grating with high precision. According to the main factors that affect the performance of the grating tiling, a 5-DOF ultraprecision stage is developed for the grating tiling experiment. The mechanism is formed by serial structures. The motion of the mechanism is guided by flexure hinges and driven by piezoelectric actuators and the movement resolution of which can achieve nanometer level. To keep the stability of the mechanism, capacitive position sensors with nanometer accuracy are fixed on it to provide feedback signals with which to realize closed-loop control, thus the positioning precision of the mechanism is within several nanometers range through voltage control and digital PID algorithm. Results of experiments indicate that the performance of the mechanism can meet the requirement of precision for grating tiling.}

阵列光栅压缩器的空域特性

引入角度偏差、位移偏差作为拼接光栅系统的物理参数，定义了拼接光栅的孔径函数，利用傅里叶角谱理论研究了高斯脉冲入射拼接光栅压缩器后的远场分布特性。研究表明；出射脉冲仍然是高斯型脉冲，但包络中心发生偏移，偏移量由角度偏差量和光束口径决定；位移偏差引入的相位随着拼接光栅压缩器传递，其对远场焦斑的影响，取决于每片子光栅的非整数倍光栅常数的横向位移偏差和纵向位移偏差的综合作用。通过数值计算得到了各维偏差对阵列光栅压缩器空域特性的影响，计算表明：光栅面外角度偏差（俯仰左右）和条纹平行度偏差都必须控制在1μrad以内，

Encoded cell grating array in anti-counterfeit technology

The dot matrix hologram (DMH) has been widely used in anti-counterfeiting label. With the same technology and cell array configuration, we can encode to the incidence beam. These codes can be some image matrix grating with different grating gap and different grating orientation. When the multi-level phase diffractive grating is etched, the incidence beam on the cell appears as an encoding image. When the encoded grating and DMH are used in the same label synchronously, the technology of multi-encoded grating array enhances the anti-counterfeit ability.

一种基于衍射光栅光束质量M^2因子的实时检测技术

提出了一种新的光束质量膨因子实时检测技术，利用一个普通正交衍射光栅组将一束待测激光束分成3×3共9路光，并利用光路调整器使9路光束通过不同的光程后有序地排列在CCD相机的探测面上，并使得各路光的光程差分布在束腰附近两倍瑞利距离内，从而可利用单一CCD探测面来同时获取待测光束多个位置上的光斑图样。再利用二阶矩理论求出各个位置上的光束束宽，通过曲线拟合进而实现光束质量的实时检测。结果表明，对于连续He-Ne激光器的输出光束，采用实时检测技术得到的测量结果与用传统方法得到的结果基本一致。

Characteristics of high reflection mirror with an SiO2 top layer for multilayer dielectric grating

The high reflection (HR) mirror composed of dielectric stacks with excellent spectrum characteristics and high damage resistant ability is critical for fabricating multilayer dielectric (MLD) grating for pulse compressor. The selection of the SiO2 material as the top layer of the HR mirror for grating fabrication is beneficial for improving the laser-induced damage threshold of MLD grating as well as minimizing the standing-wave effect in the photoresist during the exposure process. Based on an (HLL) H-9 design comprising quarter-waves of HfO2 ( H) and half-waves of SiO2 ( L), we obtain an optimal design of the HR mirror for MLD grating, the SiO2 top layer of which is optimized with a merit function including both the diffraction efficiency of the MLD grating and the electric field enhancement in the grating. Dependence of the performance of the MLD grating on the fabrication error of the dielectric mirror is analysed in detail. The HR mirror is also fabricated by E-beam evaporation, which shows good spectral characteristics at the exposure wavelength of 413 nm and at the operation wavelength of 1053 nm and an average damage threshold of 10 J cm(-2) for a 12 ns pulse.

Reusable, robust, and accurate laser-generated photonic nanosensor.

Developing noninvasive and accurate diagnostics that are easily manufactured, robust, and reusable will provide monitoring of high-risk individuals in any clinical or point-of-care environment. We have developed a clinically relevant optical glucose nanosensor that can be reused at least 400 times without a compromise in accuracy. The use of a single 6 ns laser (λ = 532 nm, 200 mJ) pulse rapidly produced off-axis Bragg diffraction gratings consisting of ordered silver nanoparticles embedded within a phenylboronic acid-functionalized hydrogel. This sensor exhibited reversible large wavelength shifts and diffracted the spectrum of narrow-band light over the wavelength range λpeak ≈ 510-1100 nm. The experimental sensitivity of the sensor permits diagnosis of glucosuria in the urine samples of diabetic patients with an improved performance compared to commercial high-throughput urinalysis devices. The sensor response was achieved within 5 min, reset to baseline in ∼10 s. It is anticipated that this sensing platform will have implications for the development of reusable, equipment-free colorimetric point-of-care diagnostic devices for diabetes screening.