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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 aims of this work were to highlight changing trend in the nonlinear optical (NLO) behaviour of ruthenium alkynyl complexes on structure modification. Chapter 1 discusses the theoretical background of NLO properties. This is followed by a brief review on the research that has been conducted in the field of organometallic NLO materials. Chapter 2 is concerned with the synthesis of a series of ruthenium bis-alkynyl complexes varying in ligand composition by chain lengthening and/or changing the arylalkynyl para-substituted functional groups, together with their cyclic voltammetric data and linear optical data. Chapter 3 discusses the strategies for synthesizing wedges with ABC composition and their use in the syntheses of dendrimers with C3subh -symmetry. A series of alkynylruthenium dendrimers with different peripheral groups was made. The electrochemical properties of these dendrimers were assessed, and the linear optical and cubic nonlinear optical properties were studied. Chapter 4 examines the effect of the number of ruthenium centers on dendrimer NLO behaviour. Mono-ruthenium, bi-ruthenium and tri-ruthenium dendrons were synthesized and their linear optical properties studied. Chapter 5 focuses on the electronic communication between ruthenium centers in multi-ruthenium alkynyl complexes. A series of linear and branched ruthenium alkynyl complexes was made. Electrochemical and linear optical properties were examined.
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 interaction of light with a nonlinear optical (NLO) material gives rise to new optical fields with altered properties (e.g. phase, frequency, amplitude, polarization, path, etc.), which are of utmost importance for photonic applications. The search for new efficient NLO materials for applications has thus been accelerated. In particular, interest in the NLO properties of organometallic systems has undergone enormous growth in the past decade. This thesis consists of a compilation of several papers relating to the experimental and density functional theory (DFT) studies of the nonlinear optical properties of metal alkynyl complexes. Paper 1 includes a brief introduction to nonlinear optical phenomena, in particular to the second-order NLO effects, and the popular experimental and quantum chemical methods for the determination of molecular first hyperpolarizability. It also includes a comprehensive review of previous semi empirical and DFT NLO calculations relating to organometallic complexes. Paper 2 deals with the benchmarking of DFT methods for first hyperpolarizabilities and excitation energies of metal alkynyls against the relevant experimental data. Papers 3-9 are combined experimental and computational (DFT) studies of dipolar (paper 3-8) and octupolar (paper 9) metal alkynyl complexes. The contribution from the calculations to each paper is as follows. In paper 3, linear optical and quadratic nonlinear optical properties of alkynyl complexes with different ligated metal centres (Ru, Ni, and Au) and with different bridges (phenylene, naphthalenylene, and anthracenylene) are calculated with DFT and time dependent DFT (TD-DFT). In paper 4, the linear optical and quadratic nonlinear optical properties of ruthenium alkynyl complexes with oligo(phenylenevinylene) bridges were calculated using DFT and the results compared with the experimental data. In paper 5, the experimentally determined linear optical properties and first hyperpolarizabilities of some ruthenium alkynyl complexes with yne/ene/azo inter-ring linkers are rationalized by DFT/TD-DFT calculations. In paper 6, the structural, linear optical, and nonlinear optical properties of ruthenium alkynyl complexes with P-P (= dppf, dppb, and dppe) and N-N (4,4'-di-tert-butyl-2,2'-bipyridine) donor co-ligands were rationalized from DFT calculations. Paper 7 consists of TD-DFT calculations undertaken on a series of bis(alkynyl) Ru complexes to rationalize the experimental linear optical data. In paper 8, the mechanism of two-dimensional NLO character in Y-shaped ruthenium alkynyl complexes is studied with the use of DFT/TD-DFT calculations. In paper 9, computational studies were undertaken to assign the key optical transitions for some octupolar compounds bearing (N-heterocyclic carbene) gold or diphenylamino substituents at the periphery.
Organometallic complexes have proven to have significant nonlinear optical (NLO) properties. They possess great design flexibility; the metal, oxidation state, ligand environment and geometry can all be varied, they may be strong oxidizing or reducing agents, and they are often able to undergo facile NLO switching. Metal alkynyl complexes form an important group of organometallic complexes that have high potential in NLO material applications. The focus of the current study is to establish structure-property relationship for ruthenium alkynyl complexes incorporating chiral R,R-Chiraphos co-ligands, and to compare the behavior of these complexes to those of analogous complexes containing the archetypical co-ligand 1,2-bis(diphenylphosphino)ethane (dppe), one of the most widely-employed diphosphine ligands in this field. Chapter 1 presents an introduction to nonlinear optics and reviews organic, inorganic and organometallic compounds for which nonlinear optical responses have been measured. Chapter 2 covers the synthesis of linear ruthenium alkynyl complexes incorporating R,R-Chiraphos. Their crystal structures, electrochemical and spectroelectrochemical properties, circular dichroism responses, and linear and quadratic nonlinear optical properties are reported. Chapter 3 reports the synthesis of ruthenium alkynyl dendrimers incorporating R,R-Chiraphos. The crystal structures, electrochemical properties, linear optical properties and circular dichroism responses of selected examples have been carried out.
Since the discovery of nonlinear effects, both the theory and measurement techniques have been developed significantly, especially since the invention of the laser. However, structure-NLO property relationships for organometallics as well as their NLO mechanisms are far less explored than those of organic molecules and inorganic salts. The greater flexibility and exceptionally large NLO responses of organometallic compounds attracts chemists to this field. Modification of coordinated co-ligands in organometallic systems has influence on the NLO merit by introducing new electronic charge-transfer transitions, oxidation state and coordination sphere of the metal centers. In this work, the donor sets of the ruthenium complexes were modified from the most investigated (P-P)(P-P) to (N-N)(P-P) and (N-P)2 and a series of ruthenium complexes were synthesized and characterized. In Chapter 2, the study of the Ru(N-N)(P-P) complexes is detailed. Three bidentate diphosphine ligands (dppe, dppb and dppf) and one diimine ligand (tert-Bu-bpy) were selected for this study as the diphosphine and diimine ligands, respectively. Ruthenium halide and mono-alkynyl complexes were obtained successfully. Their optical, electrochemical and spectroelectrochemical properties were examined and are discussed. The formation of eta3- and eta1-butenynyl complexes was confirmed by single-crystal X-ray diffraction. Attempts towards bis-alkynyl complexes were made, but no conclusive evidence could be obtained to confirm the successful synthesis of this species. In Chapter 3, the focus of the work is the study of ruthenium complexes with a (N-P)2 donor set. Two iminophosphine ligands, 2-(diphenylphosphino)pyridine (PPh2py) and 8-(diphenylphosphino)quinoline (PPh2qn), were selected for this study. The cis-RuCl2(N-P) complexes and the corresponding dimers were synthesized and characterized. Their optical and electrochemical properties were measured and are discussed. In Chapter 4, the quadratic and cubic nonlinear optical properties of organometallic complexes were explored by hyper-Rayleigh scattering (HRS) and frequency-depentdent Z-scan techniques, respectively. The first hyperpolarizabilities of the ruthenium halide and mono-alkynyl complexes described in Chapter 2 were determined by HRS measurements. The second hyperpolarizabilities of some organometallic complexes synthesized by the Humphrey group and the collaborators were measured by the Z-scan technique.
Ruthenium compounds have shown very good second order and third order behaviour. Very high non-linear optical (NLO) response is due to the extensive coordination and organometallic chemistry of ruthenium. Electron-rich d6 ruthenium (II) centres are especially well-suited for incorporation into NLO chromophores because their highly polarizable d orbitals can cause effective -electron-donating properties when coordinated to ligands with low-lying * orbitals. This work provides an understanding of the NLO properties of ruthenium complexes. All systems display large second-order NLO response. This effort may provide the guidelines to synthesize the high-performance NLO materials. The present investigation gives insight into the NLO response of ruthenium complexes and endeavors to disclose the origin of the NLO response of this family, which is interesting and important in design and synthesis of new promising NLO materials."
The handbook comprehensively covers the field of inorganic photochemistry from the fundamentals to the main applications. The first section of the book describes the historical development of inorganic photochemistry, along with the fundamentals related to this multidisciplinary scientific field. The main experimental techniques employed in state-of-art studies are described in detail in the second section followed by a third section including theoretical investigations in the field. In the next three sections, the photophysical and photochemical properties of coordination compounds, supramolecular systems and inorganic semiconductors are summarized by experts on these materials. Finally, the application of photoactive inorganic compounds in key sectors of our society is highlighted. The sections cover applications in bioimaging and sensing, drug delivery and cancer therapy, solar energy conversion to electricity and fuels, organic synthesis, environmental remediation and optoelectronics among others. The chapters provide a concise overview of the main achievements in the recent years and highlight the challenges for future research. This handbook offers a unique compilation for practitioners of inorganic photochemistry in both industry and academia.
Organometallic chemistry is based on the reactions and use of a class of compounds (R-M) that contain a covalent bond between carbon and metal. They are prepared either by direct reaction of the metal with an organic compound or by replacement of a metal from another organometallic substance. This book presents research in this field.