Inorganic Thermochromism

ISBN-13: 9783642510199 / Angielski / Miękka / 2012 / 134 str.

Kozo Sone; Yutaka Fukuda

Opis

Even brilliant colors are all bound to scatter, Who in our changing world can stay forever? From Iroha-uta, ancient Buddhistic poem of Japan For many years we have been engaged in the preparation and characterization of new metal complexes and chelates, and especially the interpretation of their electronic spectra in solutions. In the course of these studies, we have encountered a number of strange changes in color which occur upon heating, cooling or compressing the solutions, or changing the nature of the solvent. Similar effects of temperature and pressure on the color were often also observed in the solid state. Records of visual observations, spectral measurements, and their interpretations and analyses accumulated each year, until we found ourselves, quite suddenly, in the middle of a fantastic world of color changes - the world of inorganic thermochromism and related chromo tropic phenomena. This book is a result of the reviews by Sone and Prof. S. Utsuno (Kagaku no Ryoiki, 22, 222 (1968); Bunko Kenkyu, 25,123 (1976)), and a series of papers by Fukuda, Sone et al. published in the 1. Inorg. Nucl. Chern., Bull. Chern. Soc. Japan, and various other journals after 1970.

Spis treści

A. Introduction.- A.I Definition of “Inorganic Thermochromism” and the Aim of this Book.- A.II Some Common Examples of Inorganic Thermochromism.- A.II.1 NO2—N2O4 Equihbrium in the Gas Phase.- A.II.2 Color of Iodine in Various Solutions.- A.II.3 Ruby and Some Compounds of Mercury and Silver.- References.- B. Thermochromic and Chromotropic Phenomena of Cobalt(II) Chloride Solutions and Related Systems.- B.I Introductory Remarks: Visual Observations on Aqueous and Alcoholic Solutions of Cobalt(II) Chloride.- B.II Low-Temperature Spectrophotometric Studies on Alcoholic Solutions of Cobah(II) Chloride.- B.III Effects of Water, High Pressure and Dilution on the Spectra of Alcoholic Solutions of Cobalt(II) Chloride.- B.IV Thermochromic Equilibria of Cobalt(II) Chloride in Aqueous Solutions.- B.IV.1 General Remarks and “Inert Salt Effect”.- B.IV.2 Thermochromism of Cobalt(II) Chloride in Reversed Micelles.- B.V Chromotropic Phenomena of Cobalt(II) Chloride in Aprotic Solvents.- B.VI Chromotropic Phenomena of Other Cobalt(II) Salts in Aqueous and Organic Solvents.- B.VII Chromotropic Phenomena of Copper(II) and Nickel(II) Halides in Solution.- References.- C. Thermochromism of Nickel(II) Chelates in Solution.- C.I Introduction.- C.II Tetrammine-type Chelates: Octahedral-Square Planar Equilibria.- C.III ß-Diketonate Chelates: Monomer-Polymer Equilibria.- C.IV Mixed Diamine-ß-Diketonate Chelates: Solvatochromic and Thermochromic Equilibria Governed by the Coordinating Power (Donor Number) of the Solvent.- C.IV.1 Introduction.- C.IV.2 Chelate Perchlorates and Tetraphenylborates.- C.IV.3 Nitrato- and Bis(?-diketonato)-Complexes.- C.IV.4 Halogeno- and Pseudohalogeno-Complexes.- C.V Chelates of Schiff Bases and Related Ligands: Tetrahedral-Square Planar Equilibria.- C.VI Thermochromic Systems Involving Formation of Five-Coordinate Complexes and Linkage Isomerization.- C.VI.1 Formation of Five-Coordinate Complexes.- C.VI.2 Isomerization Equihbria: The Nitro-Nitrito Equilibria.- References.- D. Chromotropic Phenomena of Copper(II) Chelates.- D.I Introduction: Structure and Spectra of Copper(II) Chelates.- D.II Acetylacetonates and Tetrammine-type Complexes.- D.II.1 Acetylacetonates: Solvatochromism, Thermochromism and Gas-Phase Spectra.- D.II.2 Tetrammine-type Complexes.- D.III Mixed Diamine-?-Diketonate Chelates.- D.III.1 Introduction.- D.III.2 Chelate Perchlorates and Nitrates: Solute-Solvent Interactions.- D.III.3 Halogeno- and Pseudohalogeno-Complexes: Solute-Solute-Solvent Interactions.- References.- Ë. Miscellaneous Chromotropic Phenomena Observed in Solutions of Metallic Complexes.- E.I Introduction.- E.II Spin-Crossover in Iron(II) and Iron(III) Complexes Observed as Solution Thermochromism.- E.III Iron(II) Cyanide-(Heterocyclic N-Base) Mixed Complexes: Solvatochromism Caused by Acceptor Solvents and Ions.- E.IV Solvatochromism of Oxovanadium(IV) ?-Diketonates.- E.V Thermochromism of Metal Chelates with Triphenylmethane Complexones in Aqueous Solutions.- E. VI Thermochromism and Solvatochromism Accompanied by the Formation of Ligand Radicals in Solution.- References.- F. Thermochromism of Transition Metal Complexes in the Solid State.- F.I Introduction.- F.II Irreversible Thermochromism.- F.II.1 Visual and Spectral Observations of the Color Changes.- F.II.2 Irreversible Thermochromism Caused by Dehydration.- F.II.3 Diamine Complexes of Nickel(II): Octrahedral-Square Planar Changes with Deaquation and Anation.- F.II.4 Decomposition and Isomerization of Chromium(III) Complexes.- F.III Reversible Thermochromism.- F.III.1 Halide Complexes of Copper(II) and Nickel(II).- F.III.1.1 Thermochromism Associated with the Tetrahedral-Square Planar Changes of [CuCl4]2- and Related Complexes.- F.III.1.2 Thermochromism Associated with the Octahedral-Tetrahedral Changes of [NiCl4]2- and Related Complexes.- F.III.2 Thermochromism of the Chelates of Copper(II) and Nickel(II) with Specific Stereochemistries.- F.III.2.1 Thermochromism of the Copper(II) Chelates of[CuN4]-Type.- F.III.2.2 Thermochromism of the Nickel(II) Complexes of Some Heterocychc N-Ligands due to Monomer-Dimer Equilibria.- F.III.3 Miscellaneous Examples of Solid-State Thermochromism.- F.III.4 Fluorescence Thermochromism of Cu(I) Complexes.- F.IV Practical Applications of Solid-State Thermochromism: Color Indicators for Temperature Changes.- References.- Concluding Remarks.