Progress in Inorganic Chemistry, Volume 48

605 Pages·1999·14.045 MB·English

Progress in
Inorganic Chemistry
Volume 48
Advisory Board
JACQUELINE K. BARTON
CALIFORNIA INSTITUTE OF TECHNOLOGY, PASADENA, CALIFORNIA
THEODORE J. BROWN
UNIVERSITY OF ILLINOIS, URBANA, ILLINOIS
JAMES P. COLLMAN
STANFORD UNIVERSITY, STANFORD, CALIFORNIA
F. ALBERT COTTON
TEXAS A & M UNIVERSITY, COLLEGE STATION, TEXAS
ALAN H. COWLEY
UNIVERSITY OF TEXAS, AUSTIN, TEXAS
RICHARD H. HOLM
HARVARD UNIVERSITY, CAMBRIDGE, MASSACHUSETTS
EIICHI KIMURA
HIROSHIMA UNIVERSITY, HIROSHIMA, JAPAN
NATHAN S. LEWIS
CALIFORNIA INSTITUTE OF TECHNOLOGY, PASADENA, CALIFORNIA
STEPHEN J. LIPPARD
MASSACHUSETTS INSTITUTE OF TECHNOLOGY, CAMBRIDGE,
MASSACHUSETTS
TOBIN J. MARKS
NORTHWESTERN UNIVERSITY, EVANSTON, ILLINOIS
EDWARD I. STIEFEL
EXXON RESEARCH & ENGINEERING CO., ANNANDALE, NEW
JERSEY
KARL WIEGHARDT
MAX-PLANCK-INSTITUT, MULHEIM, GERMANY
PROGRESS IN
INORGANIC CHEMISTRY
Edited by
KENNETH D. KARLIN
DEPARTMENOTF CHEMISTRY
JOIINS HOPKINS UNIVERSITY
BALTIMOREM, ARY.IA N11
VOLUME 48
AN INTERSCIENCE" PUBLICATIQN
JOHN WILEY & SONS, INC.
New York Chichester Weinheim Brisbane Singapore Toronto
Cover Illustration of “a molecular femc wheel” %as adapted from Taft, K. L. and Lippard, J.,
S.
J. Am. Chem. Soc.. 1990, 112, 9629.
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Copyright 0 1999 by John Wiley & Sons. Inc. All rights reserved.
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Lihrary of Congress Catalog Card Number 59-1 3035
ISBN 0-471-32623-2
Printed in the United States of America
1 0 9 8 7 6 5 4 3 21
Contents
Synthesis, Structure, and Properties of Organic-Inorganic
Perovskites and Related Materials 1
DAVIDB . MITZI
IBM T J. Watson Research Centel; PO Box 218, Yorktown
Heights, New York, USA
Transition Metals in Polymeric n-Conjugated Organic Frameworks 123
RICHARDP . KINGSBOROUGH, TIMOTHYM . SWAGER
Department Chemistry, Massachusetts Institute of
of
Technology
77 Massachusetts Avenue, 18-209, Cambridge, Mussachusetts,
USA
The Transition Metal Coordination Chemistry of Hemilabile Ligands 233
CAROLINE S. SIDNE. DANAA . WEINBtRGEK, CHAD A.
MIRKIN
Department of Chemistry, Northwestern UniversiQ, 2 145
Sheridan Road, Evanston, Illinois, USA
Organometallic Fluorides of the Main Group Metals Containing
the C-M-F Fragment 35 1
BALAJIR . JAGIRDARE,A MOKNF . Mumw, HERBERTW .
ROESKY
Universitat Giittingen, Tammunnstrasse 4, 0-37077 GottinKen,
Germany
Coordination Complex Impregnated Molecular Sieves-Synthesis,
Characterization, Reactivity, and Catalysis 457
PARTHAP. PAUL
Southwest Research Institute. 6220 Culehru Road, PO Drawer
28510, Sun Antonio, Texas, USA
Advances in Metal Boryl and Metal-Mediated B-X Activation
Chemistry 505
MILTONR . SMITHI1 1
Department of Chemistry, Michigan State University, East
Lansing, Michigan, USA
v
vi CONTENTS
Subject Index 569
Cumulative Index, Volumes 1-48 589
Progress in
Inorganic Chemistry
Volume 48
Synthesis, Structure, and Properties of
Organic-Inorganic Perovskites and Related
Materials
DAVID B. MITZI
IBM T J. Watson Research Center
I? 0. Box218
Yorktown Heights, NY
CONTENI’S
1. INI’RODUCTION
A. Organic-Inorganic Hybrids
B. Inorganic Perovskites
c
scope
11. ORGANIC-INORGANIC PEROVSKITE STRIJCTI:’RES
A. Three-Dimensional Systems
R. 1,ayered (100) Oriented Perovskites
1. Transition Metal Halides
2. Group 14 (IVA) Metal Halides
3. Rare Earth Metal Halides
C. Structural Transitions
D. More Complex Organic Cations
E. Polymerized Organic Layer
F. Multilayer Perovskite Structures
(i. Layered (1 10) Oriented Perovskites
€I. One-Dimensional Systems
I. Zero-Dimensional Systems
J. Summary of Structures
111. SYNTHESIS AND CRYSTAL GROWTH
A. Self-Assembling Structures
€3. Solid-State Reactivity and Melt Processing
C. Solution Chemistv
1. Simple Organic Cations
Progre.r.c in Inorganic. Chernisrty Kd. 48, Edited by Kenneth D. Karlin.
ISBN 0-471-32623-2 0 1999 John Wiley Rr Sons, Inc.
2 DAVID B. MITZI
2. Less Stable Metal Oxidation States
3. More Complex Organic Cations
Gel Techniques and Layered Growth
4.
5. Multilayer Structures
6. Cyanamide Chemistry and the (1 10) Oriented Compounds
D. Polymerization Reactions
E. Thin-Film Growth
1. Spin Coating
2. Thermal Evaporation
3. Dip Coating
IV. PROPERTIES
A. Magnetism
1. Transition Metal Halides
2. Rare Earth Metal Halides
B. Photoluminescence
1. Transition Metal Halides
2. Group 14 (IVA) Metal Halides
3. Rare Earth Metal Halides
C. Electrical Transport
D. Electroluminescence
E. Other Properties
V. CONCL.USION
ACKNOWLEDGMENTS
ABBREVIATIONS
REFERENCES
I. INTRODUCTION
A. Organic-Inorganic Hybrids
Complex structures, based on a molecular scale composite of inorganic
and organic components, provide a substantial opportunity for tailoring new
and functional materials for scientific exploration and technological appli-
cations. Inorganic materials, typically characterized by covalent and ionic
interactions, offer the potential for high electrical mobility, a wide range
of band gaps (enabling the design of insulators, semiconductors, metals,
and superconductors), interesting magnetic interactions, a range of dielectric
properties, substantial mechanical hardness, and thermal stability. Organic
molecules, which generally interact through weaker interactions such as
hydrogen bonding and van der Waals interactions, provide the possibility of
SYNTHESIS, STRUCTURE, AND PROPERTIES OF PEROVSKITES 3
Periostracum
Outer Prismatic Layer
Nacre
Myostracum
Nacre
Inner Prismatic Layer
I
I
Figure 1. Idealized cross section of a bivalve shell. The magnified views show the schematic
structure of the nacre and prismatic layers of the shell. Within each view, the white sections
of each block are the calcium carbonate crystals, whereas the black lines represent the organic
material separating the crystals. Note the very different scales for the two insets. [Adapted
from (1) and
(4).1
structural diversity, highly efficient luminescence, a large degree of polariz-
ability, plastic mechanical properties, and in some cases can even be made
conducting or superconducting. Generally, organic-inorganic hybrid research
focuses on employing the range of interactions found within organic and
inorganic chemistry to create a composite with some enhanced property rel-
ative to that achievable with either organic or inorganic materials alone, or
to combine useful properties of the two components within a single material.
In some cases, the goal is to search for new phenomena that result from the
interaction between the organic and inorganic subunits.
Nature has long made use of the beneficial properties arising from
organic-inorganic hybrids. The nacre section of a mollusk shell (Fig. l), for
example, consists of a highly organized laminated microstructure of arag-
-
onite CaCOl crystals (with a thickness of 0.25 pm) separated by a thin
(300-500 A) layer of proteinaceous organic matter. The resultant strength
and fracture toughness of this “brick and mortar” microstructure is orders of
magnitude higher than either of the constituents (1-5). The useful proper-
ties of this biological composite arise from the highly organized and appro-
priately proportioned combination of a hard brittle inorganic phase with a
soft plastic organic phase, with strong interfacial bonding between the two