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Metal alkynyl complexes are of interest for a variety of possible applications, one being their use as advanced nonlinear optical (NLO) materials. This Thesis describes the synthesis and characterization, along with computational studies, of group 8 metal alkynyl complexes, which may exhibit interesting NLO properties. Chapter 1 discusses the theoretical background of NLO properties. This is followed by a brief review of the research that has been conducted in the field of organometallic NLO materials. Chapter 2 focuses on the syntheses of group 8 metal acetylide complexes possessing dipolar and octupolar configurations. Syntheses of both linear and branched substitution on the aryl core of either homo- or heterometallic complexes are described here, as well as crystal structures. The physical properties of these complexes are examined using a range of measurements, including cyclic voltammetry, IR and UV-vis spectroscopy. Chapter 3 covers the computational studies of the synthesized and unsynthesized complexes in Chapter 2 using the time-dependent density functional theory (TD-DFT) method. The computed linear and nonlinear optical data allow for a better understanding of the molecular electronic structure responsible for the experimental data.
The section devoted to iron in this volume reflects the tremendous progress in the area. Specifically cluster chemistry, ligand transformations and detailed structural results are more prominent in COMC II. The organic chemistry of ruthenium and osmium is an area which has burgeoned during the period since the publication of COMC. This is especially true for the cluster chemistry of these elements, which have provided most of the advances in this important field. Consequently, this volume will include an update (1981-1993) of the chemistry of mono- and bi-nuclear complexes of ruthenium and osmium, with a rather more extensive treatment of tri- and tetra-nuclear complexes. This is because many of the early results in ruthenium and osmium cluster chemistry described in COMC are now much better understood and can thus be placed in a more general context. In the case of complexes containing clusters with five or more metal atoms, the coverage is essentially complete, again because this chemistry has developed during the 1980s.
This book assembles both theory and application in this field, to interest experimentalists and theoreticians alike. Part 1 is concerned with the theory and computing of non-linear optical (NLO) properties while Part 2 reviews the latest developments in experimentation. This book will be invaluable to researchers and students in academia and industry, particularlrly to anyone involved in materials science, theoretical and computational chemistry, chemical physics, and molecular physics.
The Chemistry of Ruthenium, Rhodium, Palladium, Osmium, Iridium and Platinum