This book deals with chemistry and chemical-physical effects of Zn(II)-containing metal-organics with emergence as an interdisciplinary area of coordination chemistry, blending of optical and nonlinear optical materials research; optical fiber communication and optical computing technologies; data storage techniques; image processing; dynamic holography; printers; producing of harmonic generators; optical switching and limiting devices; fluorescence materials and more. In this context, the book collects new trends, and presents for first time more recent work in the field of applied oriented design of molecular scaffolds, synthesis, optical and nonlinear optical studies of coordination compounds of Zn(II)-ion. The book is divided into four chapters. The first Chapter 1 is designed to give readers a general overview on relevance of metal-organic materials containing metal ions with completed electronic d10 configurations to mentioned above areas of applied sciences. We have chosen to introduce relationship between molecular structure and properties of zinc tris(thiourea) sulphate and its derivatives in a short Chapter 2, because of those compounds are seriously tested for an industrial scale application as NLO-phores. Chapter 3 is devoted, principally, to a correlation between molecular structure, crystal structure and chemical physical effects of Zn(II)-containing metal-organic materials, mainly part of our research work. Chapter 4 concentrates on theoretical methodological formalism of most applicable quantum chemical methods, treating optical and non-linear optical phenomena, which are base on same thematic overall organization of this part of the book. The importance of this chapter is that it refers to basic computational chemistry methodology, associated with prediction of chemical-physical effects of metal-organics in gas- and condense phase, as a crucial step defining applied oriented chemical synthesis of new coordination compounds, thus producing results relevant to their real application as materials to optical and nonlinear optical technologies. Chapter 4 can serves as methodological reference point. But the content of the book, generally, can be useful to scientific research of MSc and PhD students in “Chemistry”, which work involves fields such as coordination chemistry, applied materials research, crystal engineering, and the fourth.
Table of Contents
Chapter 1 Metal–organics of ions with completed d10 electronic configuration as NLO materials – general overview
1.1. Metal–organic complexes of carboxylates
1.2. Organic dyes as ligands in metal–organic NLO materials
1.3. N–aliphatic ligands in metal–organic NLO materials
1.4. N–heterocyclic ligands in metal–organic NLO materials
1.5. Ferrocene containing complexes as NLO materials
1.6. B–, S– and P– containing ligands in metal–organic NLO materials
1.7. Amino acids as homochiral ligands in metal–organic NLO materials
1.8. Polymer metal–organic materials
Chapter 2 Zinc tris(thiourea) sulphate and its derivatives as non–linear optical materials
2.1. Zinc tris(thiourea) sulphate as non–linear optical material
2.2. Metal–thiourea containing crystals as non–linear optical materials
Chapter 3 ZnII–containing metal–organic materials for linear and non–linear optical technologies
3.1. Metal–organic carboxylate complexes of ZnII–ion
3.2. ZnII–metal–organic complexes of N–heterocyclic ligands
3.3. ZnII–metal organics with aliphatic N–containing ligands
3.4. Porphyrin and phthalocyanine–based ZnII–metal–organic NLO materials
3.5. ZnII–complexes with organic dyes
3.6. B–, S– and P– containing ligands in metal–organic NLO materials
Chapter 4 Quantum chemical treatment of linear and non–linear optical properties of metal–organics
4.1. Linear optical properties
4.1.1. Absorption spectra
4.1.1.1. Computation of the absorption energy
4.1.1.2. Computation of absorption band–shape
4.1.1.3. Computation of absorption intensity
4.1.2. Fluorescence spectra
4.1.2.1. Computation of emission energies
4.1.2.2. Computation of fluorescence band–shape
4.1.2.3. Computation of fluorescence intensity
4.2. Nonlinear optical properties
Objectives and Topics
This work explores the chemistry and chemical-physical properties of ZnII-containing metal-organic materials, aiming to correlate molecular and crystal structures with their linear and nonlinear optical (NLO) performance for applications in modern technologies.
- Coordination chemistry of d10-configured metal ions in NLO material design.
- Structural influence of ligands (carboxylates, organic dyes, N-heterocycles) on optical properties.
- Theoretical quantum chemical modeling of linear and nonlinear optical phenomena.
- Experimental characterization via X-ray diffraction, spectroscopy, and mass spectrometry.
- Technological applications including optical fiber communication and data storage.
Excerpt from the Book
1.1. Metal–organic complexes of carboxylates
Generally, the efforts over the years have shown that benzoic acid polyfunctional derivatives, particularly those templates containing more than one –COOH structural fragment are particularly attractive scaffolds for design of metal–organic NLO materials with tunable linear optical and NLO properties due to their large ability to form diverse number of coordination modes to metal ions; large scale ionic stoichiometry due to their polydeprotonating ability; along with great diversity of 0D–3D bonding network in crystalline state. Even simply substituted derivatives such as X,Y–benzene dicarboxylic acids have remarkable ability to form mono– and polynuclear complexes, exhibiting following coordination fashion (Scheme 1.1) [37–45].
The coordination ability of 1,2–benzenedicarboxylic acid (phthalic acid) to CdII–ion has shown formation of a mononuclear complex at molar ratio metal–to–ligand 1:4 (Fig.1.5) [42,43], where the ligand acts tetradentately. The corresponding polynuclear Zn4O(1,4–benzenedicarboxylate)3 single crystal, reported in [44] (Fig. 1.6), crystallizes in a cubic space group Fm3m. ZnII–containing coordination mixed–ligand polymers with 5–nitroisophthalate [{Zn(5–nitroisophthalate)x(5–methoxyisophthalate)1–x(deuterated 4,4’–bipyridyl)}(DMF–MeOH)]n have been reported as well [45] (Fig. 1.7).
Summary of Chapters
Chapter 1: Provides a comprehensive overview of metal-organic materials containing ions with completed d10 electronic configurations and their significance in nonlinear optical (NLO) technologies.
Chapter 2: Focuses on the properties of Zinc tris(thiourea) sulphate (ZTS) and its derivatives as well-characterized materials for NLO applications.
Chapter 3: Details specific ZnII-based metal-organic materials, correlating their unique structural features with their optical and nonlinear optical performance.
Chapter 4: Presents the quantum chemical framework for predicting linear and nonlinear optical properties of metal-organic compounds through various computational methods.
Keywords
ZnII-Coordination chemistry, Mass spectrometry, Quantum chemistry, Single crystal X-ray diffraction, Materials research, Optical properties, Nonlinear optics, Metal-organics, NLO-phores, Crystal engineering, Phthalocyanine, Porphyrin, Molecular modeling, Spectroscopic analysis, Electronic transitions.
Frequently Asked Questions
What is the core subject of this publication?
The book explores the relationship between the molecular and crystal structure of ZnII-containing metal-organic materials and their chemical-physical properties, specifically in the context of their use in linear and nonlinear optical technologies.
What are the primary areas covered in the book?
The book covers coordination chemistry, the structural design of metal-organic scaffolds, experimental characterization techniques like X-ray diffraction and mass spectrometry, and theoretical quantum chemical predictions of optical properties.
What is the ultimate goal of the research presented?
The goal is to provide a reference source for predicting and designing new, multifunctional NLO materials with tunable properties suitable for industrial-scale applications.
Which scientific methodologies are employed?
The authors use a combination of synthetic chemistry, experimental characterization (X-ray crystallography, spectroscopy, mass spectrometry), and advanced computational quantum chemistry, including TDDFT and other methods for predicting NLO responses.
What topics are discussed in the main body?
The main body examines various ligand types (carboxylates, organic dyes, N-heterocycles), the specific case of ZTS, various ZnII complexes, and the theoretical formalism required to model linear and nonlinear optical phenomena.
Which keywords summarize this work?
Key terms include ZnII-coordination chemistry, NLO materials, crystal engineering, quantum chemistry, and optical spectroscopy.
How does the work address non-centrosymmetric crystal growth?
The authors discuss strategies such as utilizing chiral counter ions, incorporating mixed ligands, and spontaneous crystallization, which are essential for producing non-centrosymmetric materials required for efficient NLO response.
Why is the d10 electronic configuration significant for these materials?
Ions with a completed d10 electronic configuration are particularly advantageous for NLO materials because they often lack d-d transitions that can cause optical absorption losses in the visible region, thereby improving optical performance.
- Quote paper
- Prof. Dr. Bojidarka Ivanova (Author), Michael Spiteller (Author), 2015, Linear and nonlinear optical Zn(II)-metal-organic materials. Correlation between molecular structure, crystal structure and chemical-physical properties, Munich, GRIN Verlag, https://www.grin.com/document/310619
