Instrumental Analysis of Coordination Compounds. Volume 2 / edited by Hiroki Oshio and Graham N. Newton.

Format:

Book

Contributor:

Oshio, Hiroki, editor.

Newton, Graham N., editor.

Series:

Coordination chemistry fundamentals series ; Volume 5.

Coordination Chemistry Fundamentals Series ; Volume 5

Language:

English

Subjects (All):

Coordination compounds.

Physical Description:

1 online resource (297 pages)

Edition:

First edition.

Place of Publication:

London, England : Royal Society of Chemistry, [2024]

Summary:

Volume two of a two-part set translated from Japanese, describes the principles and practical methods of physical measurements as well as the fundamental theories for understanding the data obtained in the study of metal complexes.

Contents:

Cover

Copyright

Preface

Contents

Chapter 1 Ligand Field Theory

1.1 Introduction

1.2 Crystal Field Theory1-3

1.2.1 Orbital Energy

1.2.2 Crystal Field Splitting

1.2.3 Weak Field and Strong Field

1.2.4 Ligand Field Theory and the Tanabe-Sugano Diagram6

1.2.5 Ligand Field Parameters for Low Symmetry Field

1.3 Angular Overlap Model5

1.3.1 Additivity, Holohedrized Symmetry and Transferability

Appendix A

A.1 Brief Introduction to Group Theory1,9,10

A.2 Character Table

A.3 Representations of Atomic Orbitals

A.4 Reduction of the Reducible Representation

A.5 Direct Product

Further Reading

References

Chapter 2 Optical Spectroscopy

2.1 Introduction

2.1.1 Electronic Spectra

2.1.1.1 Measurements

2.1.1.2 Ligand Field d-d Transition Spectra

2.1.1.2.1 The Spin-allowed Transitions for High Spin Complexes

2.1.1.2.2 The Spin-allowed Transitions of the Low Spin Complexes

2.1.1.2.3 Spin-forbidden d-d Transitions

2.1.1.3 Dependence of Ligand Field Spectra on Ligands and Central Metal Ions

2.1.1.3.1 Spectrochemical Series

2.1.1.3.2 Nephelauxetic Effect

2.1.1.3.3 Two-dimensional Spectrochemical Series

2.1.1.4 Ligand Field Spectra and Stereochemistry

2.1.1.4.1 Geometrical Structures

2.1.1.4.2 Jahn-Teller Effect

2.1.1.4.3 Absorption Spectra of Tetrahedral Four Coordinate (T-4) Complexes and Square Planar Four Coordinate (SP-4) Complexes

2.1.1.4.4 Absorption Spectra of Five-coordinate Complexes

2.1.1.5 Electronic Transitions Other Than Ligand Field Transitions

2.1.1.5.1 Intraligand Electronic Transitions

2.1.1.5.2 Charge Transfer Transitions

2.1.1.5.3 Electronic Transitions of Mixed Valence Complexes

2.1.1.5.4 d-d Transitions for the Metal-Metal Bond

2.1.1.5.5 4f-4f Transitions for Lanthanide Complexes.

2.1.1.6 Absorption Band Intensities and Selection Rules

2.1.1.6.1 The Orbital Selection Rule and the Spin Selection Rule

2.1.1.6.2 Absorption Band Intensities of the Spin-allowed Transitions

2.1.1.6.3 Absorption Band Intensities of Spin-forbidden Transitions

2.1.1.6.4 The Spin-forbidden Transition Intensity Enhancement Through Magnetic Interaction

2.1.1.6.5 The Intraligand Spin-forbidden Transitions in Paramagnetic Complexes

2.1.1.6.6 Band Widths of Absorption Bands

2.1.1.7 Chromotropism28

2.1.2 Chiroptical Spectra

2.1.2.1 Circular Dichroism

2.1.2.1.1 CD in Ligand Field Transitions

2.1.2.1.2 CD in Intraligand Transitions

2.1.2.2 Circularly Polarized Luminescence (CPL)

2.1.2.3 Magnetic Circular Dichroism (MCD)

2.1.2.4 Cross Effect of CD and MCD

2.1 Electronic Spectra

2.2 Chiroptical Spectra

2.2.1 Circular Dichroism

2.2.2 Circularly Polarized Luminescence (CPL)

2.2.3 Magnetic Circular Dichroism

2.2.4 Cross Effect of CD and MCD

Magnetochiral Dichroism

Chapter 3 Acid Dissociation Constants, Formation Constants, and Other Thermodynamic Parameters

3.1 Equilibrium in Solutions

3.1.1 Stability Constants

3.1.2 Law of Conservation of Mass (Mass Balance Equation)

3.1.3 Acid Dissociation Constants of Ligands

3.1.4 Calculation of Formation Distribution from Stability Constants

3.1.5 Solvates

3.2 Determination of Stability Constants and Other Thermodynamic Parameters

3.2.1 Potentiometry

3.2.2 Stability Constant Determination by pH Titration

3.2.3 Spectrometry

3.2.4 Calorimetry

3.2.5 Rate Constants

3.3 Complexation Thermodynamics

3.3.1 Gibbs Energy and Stability Constants

3.3.2 Supporting Electrolytes and Ionic Strength

3.3.3 Enthalpy and Entropy

3.3.4 Reaction Rates and Activation State

References.

Chapter 4 Electrochemistry

4.1 Nernst Equation

4.2 Electrolyte Solution

4.2.1 Solvent

4.2.2 Supporting Electrolyte

4.3 Electrode

4.3.1 Working Electrode

4.3.2 Reference Electrode

4.3.2.1 Aqueous Reference Electrode

4.3.2.1.1 Hydrogen Electrode

4.3.2.1.2 Calomel Electrode

4.3.2.1.3 Ag/AgCl Electrode

4.3.2.2 Non-aqueous Reference Electrode

4.3.2.2.1 Ag/Ag+ Electrode

4.3.2.2.2 Internal Standard

4.3.3 Counter Electrode

4.3.4 Arrangement of Electrodes

4.3.4.1 Two-electrode System

4.3.4.2 Three-electrode System

4.3.4.3 Salt Bridge

4.4 Electric Double Layer

4.5 Potential Window

4.6 Apparatus

4.7 Charge Transfer and Diffusion Limitation

4.7.1 Charge Transfer Limitation

4.7.2 Diffusion Limitation

4.7.3 Current-Potential Curve Taking Mass Transfer Into Account

4.7.4 Reversible, Quasi-reversible, and Irreversible Systems

4.8 Measurement Techniques

4.8.1 Chronoamperometry

4.8.2 Chronocoulometry

4.8.3 Measurements with a Rotating Disk Electrode

4.8.4 Tafel Plot

4.8.5 Pulse Voltammetry

4.8.6 Cyclic Voltammetry

4.8.6.1 Theory

4.8.6.2 Example

4.8.7 Bulk Electrolysis

4.8.7.1 Potentiostatic Electrolysis

4.8.7.2 Galvanostatic Electrolysis

4.8.8 UV-visible-NIR Spectroscopy Upon Electrolysis

4.8.9 Surface Modified Electrode

Chapter 5 Calorimetry and Thermal Analysis

5.1 Thermal Analysis

5.1.1 Introduction

5.1.2 Differential Thermal Analysis and Differential Scanning Calorimetry

5.1.2.1 Theory

5.1.2.1.1 Baseline and Heat Capacity

5.1.2.1.2 Peak Area and Amount of Heat

5.1.2.1.3 Peak Height

5.1.2.1.4 Separating Peaks for Energy Determination

5.1.2.1.5 Effects of Purge Gas

5.1.2.2 Analysis

5.1.2.2.1 Temperature and Thermodynamic Order of Phase Transitions

5.1.2.2.2 Phase Relation of a Pure Compound.

5.1.2.2.3 Heat Capacity

5.1.2.2.4 Reaction Kinetics

5.1.3 Thermogravimetry

5.1.3.1 Principle

5.1.3.2 Analysis

5.1.3.2.1 Stoichiometry of Chemical Reaction and Temperature Effects

5.1.3.2.2 Reaction Kinetics Under Isothermal Conditions

5.1.3.2.3 Particle Size Distribution of One-dimensional Porous Material by Isothermal Analysis

5.1.3.2.4 Reaction Kinetics Under Constant Heating

5.2 Heat Capacity Calorimetry

5.2.1 Thermodynamic Quantities and Heat Capacity

5.2.2 Heat Capacity of Solids

5.2.3 Calorimetric Techniques

5.2.3.1 Adiabatic Calorimetry

5.2.3.2 Relaxation Calorimetry

5.2.3.3 AC Calorimetry

5.2.4 Background Heat Capacity

5.2.4.1 Naïve Extrapolation

5.2.4.2 Computational Fit

5.2.4.3 Graphical Interpolation

5.2.4.4 Computational Modelling

5.2.4.5 Use of Counter Compounds

5.2.5 Analysis of Entropy

5.2.6 Magnetic Heat Capacity

5.2.7 Glass Transition

Chapter 6 Single Crystal X-ray Structure Analysis

6.1 Introduction

6.2 Crystal Symmetry

6.2.1 Definition of Crystals

6.2.2 Crystal Lattice

6.2.3 Symmetry, Symmetry Operations, and Symmetry Elements

6.2.4 Category of Symmetry Operations

6.2.5 Crystallographic Symmetry Operations

6.2.6 Crystallographic Point Groups

6.2.7 Space Groups

6.2.8 Category of Space Groups: Point Groups, Laue Symmetry, and Crystal System

6.2.9 Point Groups and Space Groups without Inversion Centres

6.2.10 Bravais Lattice

6.3 Space Group Symbols

6.3.1 Triclinic Space Groups

6.3.2 Monoclinic Space Groups

6.3.3 Orthorhombic Space Groups

6.3.4 Tetragonal Space Groups

6.3.5 Trigonal Space Groups

6.3.6 Hexagonal Space Groups

6.3.7 Cubic Space Groups

6.3.8 International Tables

6.4 X-ray Diffraction by Crystals

6.4.1 Atomic Scattering Factors.

6.4.2 What Determines the Diffraction Patterns?

6.4.3 Bragg Condition, Face Index, and Reflection Index

6.4.4 Laue Symmetry of Diffraction Patterns and Friedel's Law

6.4.5 Anomalous Scattering, Determination of Absolute Structure, and Flack Parameters

6.5 Diffraction Data Collection

6.5.1 Wavelengths

6.5.2 Measuring Temperatures

6.5.3 Crystal Selection with Visual Inspections

6.5.4 Mounting and Centring Crystals

6.5.5 Checking the Diffraction Patterns

6.5.6 Determination of Lattice Constants

6.5.7 Deciding Measurement Conditions and Starting Measurements

6.5.8 Integration and Correction of Raw Data

6.5.9 Space Group Determinations

6.6 Determination and Refinements of Structural Models

6.6.1 Initial Phase Determinations

6.6.2 Interpretations of the Direct Method Outputs

6.6.3 Disorder

6.6.4 Least Squares

6.6.5 Judgement of Convergence

6.7 Interpretation and Assessment of Results

6.7.1 Molecular Structures

6.7.2 Assessment of the Analysis Precision

6.7.3 Plausibility of the Determined Absolute Structure

6.7.4 Atomic Displacement Parameters

6.7.5 Comparison with a Database

6.7.6 CIF

6.8 Concluding Remarks

Chapter 7 IR and Raman Spectroscopies

7.1 Introduction

7.2 Interaction Between Light and Molecules

7.3 Molecular Vibration

7.3.1 Molecular Vibration of a Diatomic Molecule

7.3.2 Molecular Vibration of a Tri-atomic Molecule2 (CO2)

7.3.3 Quantum Theory for Molecular Vibration

7.4 Molecular Symmetry

7.4.1 Point Groups C2v and C3v

7.4.2 Point Group D∞h

7.4.3 Selection Rules for IR and Raman Spectra

7.5 Resonance Raman Spectra

7.5.1 Selective Intensity Enhancement of the Resonance Raman Band

7.5.2 Which Vibrational Modes of the Chromophore Are Subject to Resonance Enhancement?

7.5.3 Porphyrin Ligand.

7.6 Research Studies.

Notes:

Description based on publisher supplied metadata and other sources.

Description based on print version record.

Includes bibliographical references and index.

ISBN:

9781837675005

1837675007

9781837674992

183767499X