[inorganic chemistry concepts] inorganic thermochromism volume 10 ||

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Inorganic Chemistry Concepts Volume 10 Editors Christian K. J0rgensen, Geneva· Michael F. Lappert, Brighton Stephen 1. Lippard, Cambridge, MA . John L. Margrave, Houston Kurt Niedenzu, Lexington· Heinrich Noth, Munich Robert W. Parry, Salt Lake City· Hideo Yamatera, Nagoya

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Page 1: [Inorganic Chemistry Concepts] Inorganic Thermochromism Volume 10 ||

Inorganic Chemistry Concepts Volume 10

Editors

Christian K. J0rgensen, Geneva· Michael F. Lappert, Brighton Stephen 1. Lippard, Cambridge, MA . John L. Margrave, Houston Kurt Niedenzu, Lexington· Heinrich Noth, Munich Robert W. Parry, Salt Lake City· Hideo Yamatera, Nagoya

Page 2: [Inorganic Chemistry Concepts] Inorganic Thermochromism Volume 10 ||

Kozo Sane, Yutaka Fukuda

Inorganic Thermochromism

With 71 Figures and 16 Tables

Springer-Verlag Berlin· Heidelberg· New York London·Paris·Tokyo

Page 3: [Inorganic Chemistry Concepts] Inorganic Thermochromism Volume 10 ||

Prof. Dr. Kozo Sone Prof. Dr. Yutaka Fukuda

Department of Chemistry Faculty of Science Ochanomizu University Otsuka 2-1-1, Bunkyo-ku, Tokyo 112 Japan

ISBN 978-3-642-51019-9 ISBN 978-3-642-51017-5 (eBook)

DOl 10.1007/978-3-642-51017-5

Library of Congress Cataloging-in-Publication Data.

Sone, Kozo, 1923- Inorganic thennochromism. (Inorganic chemistry concepts; v. 10) Bibliography: p. Includes index. 1. Thennochromism. 2. Coordination compounds. 3. Chemistry. Inorganic. I. Fukuda, Yutaka, 1943-II. Title. III. Series. QD473.S565 1987 541.3'6 87-9563

ISBN 978-3-642-51019-9

This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilms or in other ways, and storage in data banks. Duplication of this publication or parts thereof is only permitted under the provisions of the German Copyright Law of September 9, 1965, in its version of June 24, 1985, and a copyright fee must always be paid. Violations fall under the prosecution act of the German Copyright Law.

© Springer-Verlag Berlin, Heidelberg 1987 Softcover reprint of the hardcover 1st edition 1987 The use of registered names, trademarks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use.

2152/3020-543210

Page 4: [Inorganic Chemistry Concepts] Inorganic Thermochromism Volume 10 ||

Preface

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. A large part of these works has been reviewed by Sone and Fukuda in the book "Ions and Molecules in Solution" of the series "Studies in Physical and Theoretical Chemistry" (Vol. 27; Ed. N. Tanaka et aI., Elsevier (1983)). In addition to these works, we have naturally tried to review as many as possible related works in the literature. However, we discovered that a more or less complete review of such works is a very difficult task, since many of them are concerned with the spectacular changes in color occasionally found in the course of various types of research. They are therefore scattered over many different kinds of journals, and the phenomena of our interest are often only briefly mentioned or described, so that information cannot be gleaned from the titles or abstracts. Moreover, there exist only a few reviews of this particular field of inorganic chemistry; some of them are somewhat old, while the others are limited in scope. Thus, we realized that we were going to write the first book on this topic.

The writing of such a book has really been a challenge. Neither of us knew exactly how to accomplish such a feat; there was no "parent book" to follow, nor a "rival book" to compete with. Thus, we had to

Page 5: [Inorganic Chemistry Concepts] Inorganic Thermochromism Volume 10 ||

VI Preface

write the book in our own way. Above all, we tried to make the nature of the phenomena observed and their interpretations, that is, the beauty, interest and importance of such facts and theories in modern inorganic chemistry, easily understandable to readers of an under­graduate level, just as in our lectures, and did not fear the criticism of more advanced readers who may have wanted more sophistication. We collected, selected and arranged the works to be cited according to our own interest or taste, and tried to explain them in our own words which may sometimes be different from those of the original authors. Our aim always was to present a reasonably good coverage of important works, though a number of important papers could not be reviewed in a satisfactory way, and some even had to be left out. This is a regrettable situation, indeed, but was really inevitable in the treatment of such a wealth of material. However, we hope that the author(s) of the second book can fill in these gaps and do a better job.

In spite of all these defects, and the very fact that the color changes of many interesting systems (for example, those of CoCl2 solutions; cf. Chapter B) are not yet completely understood so that their descriptions had to be qualitative, or even superficial, we have finally written this book in the present style. Now it is at your disposal; we hope, very sincerely, that you can enjoy reading it with a bit of time and patience, and find something new, interesting or useful.

We are most deeply indebted to Prof. Hideo Yamatera (Nagoya Univ.) who kindly encouraged us, in 1978, to write this book as a volume of the series "Inorganic Chemistry Concepts". His lasting support, advice and suggestions concerning the content and style of the manuscript were truly invaluable in every step of our writing. We are also cordially obliged to Dr. F. L. Boschke and Dr. R. Stumpe of the Spinger-Verlag for their friendly help and great patience, which have led us to the last page of this book after such a long time.

Our sincere thanks are also due to Prof. Masayoshi Nakahara (St. Paul's Univ., Tokyo) and Prof. Motoharu Tanaka (Nagoya Univ.), who reviewed the manuscript and supplied many valuable tips to improve the text, and to Prof. Masatoshi Fujimoto (Hokkaido Univ., Sapporo), Prof. Masayasu Mori (Osaka City Univ.), and Prof. Junzo Sunamoto (Nagasaki Univ.), for their helpful comments.

We cannot forget the hospitality of Prof. Viktor Gutmann, Prof. Ulrich Mayer, Prof. Roland Schmid and Dr. Rudolf W. Soukup (Technische Univ. Wien), shown to both of us during our visits to Vienna in 1983-1984. For their warmheartedness and friendly interest in our book we would like to say "vielen herzlichen Dank".

We would also like to thank all of our collaborators in this field, especially Dr. Tominosuke Katsurai, Prof. Michinobu Kato (Aichi Prefectural Univ. Nagoya) and Prof. Shunji Utsuno (Shizuoka Univ.) who worked with Sone on his earlier thermochromic studies, and Prof. Kenzo Nagase (Tohoku Univ., Sendai) for his recent collaboration.

Page 6: [Inorganic Chemistry Concepts] Inorganic Thermochromism Volume 10 ||

Preface VII

Again we are thankful for the contributions made by the graduate and undergraduate students of Ochanomizu University, who worked with us in the past seventeen years. Nearly nothing could have been accomplished in our small laboratory without their support, filled with wisdom and devotion. Indeed, even this book could never have been written without them.

Tokyo, September 1987 Kozo Sone Yutaka Fukuda

Page 7: [Inorganic Chemistry Concepts] Inorganic Thermochromism Volume 10 ||

Contents

Chapter A. Introduction . . . . . . . . . . . . . . . .. 1

A.l Definition of "Inorganic Thermochromism" and the Aim of this Book. . . . . . . . . . . . . . .. 1

All Some Common Examples of Inorganic Thermochromism. . . . . . . . . . 2

AII.1 N02-N20 4 Equilibrium in the Gas Phase. 2 A.II.2 Color of Iodine in Various Solutions . . . 4 AII.3 Ruby and Some Compounds of Mercury and Silver 8 References. . . . . . . . . . . . . . . . . . . . . 11

Chapter B. Thermochromic and Chromotropic Phenomena of Cobalt(II) Chloride Solutions and Related Systems 13

B.I Introductory Remarks: Visual Observations on Aqueous and Alcoholic Solutions ofCobalt(II) Chloride 13

B.II Low-Temperature Spectrophotometric Studies on Alcoholic Solutions of Cobalt(I1) Chloride . . .. 15

B.I11 Effects of Water, High Pressure and Dilution on the Spectra of Alcoholic Solutions of Cobalt(lI) Chloride. . . . . . . . . . . . . . . . . . 20

B.IV Thermochromic Equilibria of Cobalt(II) Chloride in Aqueous Solutions . . . . . . . . . . 25

B.IV.l General Remarks and "Inert Salt Effect". . 25 B.IY.2 Thermochromism of Cobalt(lI) Chloride in

Reversed Micelles. . . . . . . . . . . . 29 B.V Chromo tropic Phenomena of Cobalt(lI) Chloride in

Aprotic Solvents . . . . . . . . . . . . . .. 32 B.VI Chromotropic Phenomena of Other Cobalt(lI) Salts

in Aqueous and Organic Solvents. . . . . . .. 35 B.VII Chromo tropic Phenomena ofCopper(lI) and Nickel(II)

Halides in Solution 37 References. . . . . . . . . . . . . . . . . . . . . . . 40

Chapter C. Thermochromism of Nickel(II) Chelates in Solution 43

C.I Introduction . . . . . . . . . . . . . . . . . . 43 C.II Tetrammine-type Chelates: Octahedral-Square Planar

Equilibria . . . . . . . . . . . . . . . . . . . 43

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X Contents

C.Ill C.IV

C.IV.1 C.IV.2 C.IV.3

~-Diketonate Chelates: Monomer-Polymer Equilibria Mixed Diamine-~-Diketonate Chelates: Solvatochromic and Thermochromic Equilibria Governed by the Coordinating Power (Donor Number) of the Solvent. . . . . . . Introduction . . . . . . . . . . . . . . . Chelate Perchlorates and Tetraphenylborates . Nitrato- and Bis(~-diketonato)-Complexes . .

C.IV.4 Halogeno- and Pseudohalogeno-Complexes C.V Chelates of Schiff Bases and Related Ligands:

50

53 53 54 61 62

C.VI 64 Tetrahedral-Square Planar Equilibria . . . .

Thermochromic Systems Involving Formation of Five-Coordinate Complexes and Linkage Isomerization 67

C.VI.1 Formation of Five-Coordinate Complexes . 67 C.VL2 Isomerization Equilibria: The Nitro-Nitrito

Equilibria 68 References. . . . . . . . . . . . . . . . . . . 70

Chapter D. Chromotropic Phenomena of Copper(II) Chelates 72

D.I

D.II D.II.1

D.II.2 D.Ill D.III.l D.III.2

Introduction: Structure and Spectra of Copper(II) Chelates. . . . . . . . . . . . . . . . . . . Acetylacetonates and Tetrammine-type Complexes. Acetylacetonates: Solvatochromism, Thermochromism and Gas-Phase Spectra Tetrammine-type Complexes . . . . . Mixed Diamine-~-Diketonate Chelates. Introduction . . . . . . . . . . Chelate Perchlorates and Nitrates:

72 74

74 78 81 81

Solute-Solvent Interactions. . . . 81 D.III.3 Halogeno- and Pseudohalogeno-Complexes:

Solute-Solute-Solvent Interactions. 84 References. . . . . . . . . . . . . . . . . . . 90

Chapter E. Miscellaneous Chromotropic Phenomena Observed in Solutions of Metallic Complexes. . . . . . .. 92

E.I Introduction . . . . . . . . . . . . . . . .. 92 E.II Spin-Crossover in lron(II) and lron(Ill) Complexes

Observed as Solution Thermochromism . . . .. 92 KIll Iron(II) Cyanide-(Heterocyc1ic N-Base) Mixed

Complexes: Solvatochromism Caused by Acceptor Solvents and Ions. . . . . . . . . . . . . .. 94

E.IV Solvatochromism of Oxovanadium(IV) ~-Diketonates 98 E.V Thermochromism of Metal Chelates with

Triphenylmethane Complexones in Aqueous Solutions . . . . . . . . . . . . . . . . . . . 101

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Contents XI

E.VI Thermochromism and Solvatochromism Accompanied by the Formation of Ligand Radicals in Solution 0 102

References 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 103

Chapter F. Thermochromism of Transition Metal Complexes in the Solid State 104

F.I Introduction 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 104 F.II Irreversible Thermochromism 0 0 0 0 0 0 0 0 105 F.l1.1 Visual and Spectral Observations of the Color

Changes 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 105 F.llo2 Irreversible Thermochromism Caused by

Dehydration 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 108 F.II.3 Diamine Complexes of Nickel(II):

Octrahedral-Square Planar Changes with Deaquation and Anation 0 0 0 0 0 0

F.IIA Decomposition and Isomerization of Chromium(III) Complexes 0 0 0 0 0

F.III Reversible Thermochromism 0 0 0 0

F.III.1 Halide Complexes of Copper(lI) and Nickel(lI) F.IIl.l.1 Thermochromism Associated with the

Tetrahedral-Square Planar Changes of [CuCI4]2-

112

115 116 116

and Related Complexes 0 0 0 0 0 0 0 0 0 0 0 0 0 116 F.II1.1.2 Thermochromism Associated with

the Octahedral-Tetrahedral Changes of [NiCI4 ] 2 - and Related Complexes

F.III.2 Thermochromism of the Chelates of Copper(lI) and Nickel(lI) with Specific Stereochemistries 0

F.II1.2.1 Thermochromism of the Copper(lI) Chelates of [CuN4J-Type 0 0 0 0 0 0 0 0 0 0 0 0 0

F.III.2.2 Thermochromism of the Nickel(II) Complexes of Some Heterocyclic N-Ligands due to Monomer-Dimer Equilibria 0 0 0 0 0

F.III.3 Miscellaneous Examples of Solid-State

119

121

121

125

Thermochromism 0 0 0 0 0 0 0 0 0 0 126 F.II1.4 Fluorescence Thermochromism of Cu(I) Complexes 128 F.IV Practical Applications of Solid-State

Thermochromism: Color Indicators for Temperature Changes 0

References 0 0 0 0 0

Concluding Remarks 0

Subject Index 0 0 0 0

128 130

132

133