Silicon-containing dendritic polymers

434 Pages·2009·35.25 MB·English

by  Petar R. Dvornic, Michael J. Owen (auth.), Petar R. Dvornic, Michael J. Owen (eds.)

Silicon-Containing Dendritic Polymers
ADVANCES IN SILICON SCIENCE
volume 2
Series Editor:
JANIS MATISONS
School of Chemistry, Physics and Earth Sciences, Flinders University, South Australia.
Advances in Silicon Science is a book series which presents reviews of the present and
future trends in silicon science and will benefit those in chemistry, physics, biomedical engi-
neering, and materials science. It is aimed at all scientists at universities and in industry who
wish to keep abreast of advances in the topics covered.
Series Editor
Professor Janis Matisons
Nanomaterials Group
Chair of Nanotechnology
School of Chemistry, Physics and Earth Sciences
Flinders University
GPO Box 2100,
Adelaide 5001
SOUTH AUSTRALIA
Volume 2
Silicon-Containing Dendritic Polymers
Volume Editors
Dr. Petar R. Dvornic
Michigan Molecular Institute
1910 W. St. Andrews Rd.
Midland, MI 48640
USA
Dr. Michael J. Owen
Michigan Molecular Institute
1910 W. St. Andrews Rd.
Midland, MI 48640
USA
For other titles published in this series, go to http://www.springer.com/series/7926
Petar R. Dvornic (cid:129) Michael J. Owen
Editors
Silicon-Containing
Dendritic Polymers
Editors
Petar R. Dvornic Michael J. Owen
Michigan Molecular Institute Michigan Molecular Institute
1910 W. St. Andrews Rd. 1910 W. St. Andrews Rd.
Midland, MI 48640 Midland, MI 48640
USA USA
[email protected] [email protected]
ISBN: 978-1-4020-8173-6 e-ISBN: 978-1-4020-8174-3
DOI: 10.1007/978-1-4020-8174-3
Library of Congress Control Number: 2008936828
© 2009 Springer Science + Business Media B.V.
© Chapter 3 is published with kind permission of © Her Majesty the Queen in Right of Canada 2009
No part of this work may be reproduced, stored in a retrieval system, or transmitted in any form or by any
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Preface
In this book, we have attempted to present a coherent picture of the field of silicon-
containing dendritic polymers which has attracted outstanding research attention
during the last 20 years. This interest resulted from an almost explosive develop-
ment of dendritic polymers in general, including primarily dendrimers and hyper-
branched polymers, which have become one of the fastest growing areas of polymer
science, and from a unique combination of properties of silicon-containing poly-
mers that is not found in any class of “purely” organic materials.
The almost contagious fascination of many scientists from different disciplines
with dendritic polymers came mostly from their unprecedented molecular architec-
ture, unique resulting properties and the realization that they represent ideal build-
ing blocks for “soft”, chemical, bottom-up nanotechnology. As a consequence,
several hundred different dendritic polymer families have been reported, among
which the silicon-containing ones (similar to the situation in other fields of polymer
science, including linear and crosslinked polymers) have attracted most of the
attention among the non-fully-organic members of this polymer family (i.e., those
containing element(s) other than C, H, N and O).
Appropriately, siloxane dendrimers were the first heteroatom dendritic polymers
to be reported as early as 1989 by the founders of the field, Evgenij Rebrov and
Aziz Muzafarov of the Institute of Synthetic Polymer Materials of the Russian
Academy of Sciences in Moscow. Since then, many other types of related materials
have been described including carbosilane, silane and silazane dendrimers, as well
as their copolymeric counterparts. In all of these, silicon has been used as an ideal
branching junction with the rare ability to provide controllable branching function-
ality of either two or three, resulting in a plethora of new materials with properties
that are not attainable in any other way.
It is a special feature of this book, which is the first on this subject matter, that
it compiles the developments in each of the major areas of the field of silicon-
containing dendritic polymers as seen through the eyes of those who were either the
pioneers who initially opened each area or who played one of the major roles in
their development, or both. Hence, the list of chapter authors truly is a “who’s who”
in the field of silicon-containing dendritic polymers, and we are extremely grateful
to all of them for accepting our invitation to participate in this project and for deliv-
ering their masterpieces in such an excellent form and timely manner. As a result,
v
vi Preface
all chapters represent the state of the art in each individual area, meet the highest
scientific standards and contain a wealth of information and a variety of inspiring
suggestions for future developments.
This book consists of two main parts: Chapters 2–11 are devoted to the silicon-
containing dendrimers and Chapters 12–16 are devoted to the silicon-containing
hyperbranched polymers. In Chapter 1, we briefly overview the entire field of den-
dritic polymers and emphasize the role that silicon plays within it. Chapters 2–7
describe some of the most important classes of silicon-containing dendrimers,
including those primarily built on siloxane, carbosilane, silane, silazane, silyl ether
and polyhedral oligomeric silsesquioxane compositions. Chapters 8–10 present
some of the so far most successful applications of silicon-containing dendrimers,
including those in electrochemistry (of metallo-silicon dendrimers), catalysis and
liquid crystalline materials based on dendrimers with mesogenic side groups.
Chapter 11 bridges the worlds of silicon and purely organic structures in dendrimer
chemistry and it highlights unique radially layered copolymeric PAMAMOS den-
drimers which are the first commercially available silicon-containing dendrimers.
Chapters 12–15 describe the state of the art in the field of silicon-containing
hyperbranched polymers, wherein Chapter 15 addresses the very important issue of
intramolecular cyclization. Finally, Chapter 16 describes a rather unconventional
method of preparing the hyperbranched polymers by the so-called bimolecular
nonlinear polymerization derived from the classic polymer crosslinking technolo-
gies and receiving quite an interest lately.
For all these reasons, we are sure that this book will serve as a useful guide and
a source of reference for experienced scientists interested in this and related fields,
as well as for advanced graduate students either as a source of creative inspiration
or as a textbook for appropriate courses. We also believe that it will find its readers
in a variety of different interdisciplinary fields, including those of synthetic chem-
istry, polymer and materials science, silicone chemistry and technology, and par-
ticularly nanotechnology.
Finally, we wish to point out that, of course, we are entirely responsible for any
conceptual errors or omissions, and in cases where we had to make choices we
apologize to those few who we could not invite to contribute because of space limi-
tations. We also wish to thank Springer, our publishing company, and particularly
Dr. Sonia Ojo our publishing editor for expert help, understanding, and cooperation
during the preparation of the manuscript, and superb realization of the final text
during the production process.
Petar R. Dvornic
In Midland, August 2008 Michael J. Owen
Contents
1 The Role of Silicon in Dendritic Polymer Chemistry ........................... 1
Petar R. Dvornic and Michael J. Owen
1.1 Introduction ....................................................................................... 1
1.2 Dendrimers and Hyperbranched Polymers ....................................... 4
1.2.1 Dendrimers ............................................................................ 4
1.2.2 Hyperbranched Polymers ...................................................... 10
1.3 A Brief Historical Overview of the Main Developments
in Dendrimers and Hyperbranched Polymers ................................... 13
1.4 Silicon in Dendritic Polymers ........................................................... 15
2 Polysiloxane and Siloxane-Based Dendrimers ...................................... 21
Aziz Muzafarov and Evgenij Rebrov
2.1 Introduction: Historical Background................................................. 21
2.2 Chemistry of Siloxane Dendrimers ................................................... 22
2.3 Peculiarities of Siloxane Dendrimers ................................................ 25
2.4 Prospects for Further Development in the Chemistry
of Siloxane Dendrimers..................................................................... 28
3 Carbosilane Dendrimers ......................................................................... 31
Jacques Roovers and Jianfu Ding
3.1 Introduction ....................................................................................... 31
3.2 Synthesis of Carbosilane Dendrimers ............................................... 32
3.2.1 Core Molecules ..................................................................... 33
3.2.2 Interior Generations .............................................................. 38
3.2.3 Peripheral (Corona; End-Groups) Modification ................... 43
3.3 Carbosilane Dendrimer Characterization .......................................... 60
3.4 Properties of Carbosilane Dendrimers .............................................. 62
3.4.1 Molecular Dimensions of Carbosilane Dendrimers .............. 62
3.4.2 Dynamics of Carbosilane Dendrimers .................................. 66
vii
viii Contents
4 Polysilane Dendrimers ............................................................................. 75
Masato Nanjo and Akira Sekiguchi
4.1 Introduction ....................................................................................... 75
4.2 Synthetic Approaches to Polysilane Dendrimers .............................. 76
4.2.1 Convergent Methods ............................................................. 76
4.2.2 Divergent Methods ................................................................ 79
4.2.3 Double-Cored Polysilane Dendrimers .................................. 81
4.2.4 Functionalized Polysilane Dendrimers ................................. 84
4.3 NMR Spectroscopy of Polysilane Dendrimers ................................. 85
4.4 Crystallography and Conformation of Polysilane Dendrimers ......... 87
4.5 Electronic Spectra ............................................................................. 91
4.6 Conclusions and Future Outlook ....................................................... 94
5 Polycarbosilazane and Related Dendrimers
and Hyperbranched Polymers ................................................................ 97
David Y. Son
5.1 Introduction ....................................................................................... 97
5.2 Polycarbosilazane Dendrimers .......................................................... 98
5.3 Polysilazane Dendrimers .................................................................. 99
5.4 Related Dendrimers .......................................................................... 100
5.5 Hyperbranched Polycarbosilazanes .................................................. 101
5.6 Concluding Remarks ......................................................................... 102
6 Silyl Ether Containing Dendrimers with Cyclic Siloxane Cores ......... 105
Chungkyun Kim
6.1 Introduction ....................................................................................... 105
6.2 Siloxane Dendrimers with Cyclic Siloxane Core (0G(4)-Vinyl) ...... 106
6.3 Synthesis of Dendrimers with Si–O–C Units from
Cyclic Siloxane Cores ....................................................................... 108
6.3.1 General Synthetic Strategy from 0G(4)-Vinyl Core ............. 108
6.3.2 Dendrimers with Organic Functional End-Groups ............... 108
6.3.3 Dendrimers with Triple Bonds .............................................. 109
6.3.4 “Double-Layered” Dendrimers with Conjugated
Branches ................................................................................ 110
6.3.5 Ferrocenyl-Functionalized Dendrimers
as CO Gas Sensor .................................................................. 112
6.3.6 Water Soluble Dendrimers .................................................... 112
6.3.7 Dendrimers with Terpyridine Ruthenium
Complex End-Groups ............................................................ 114
6.3.8 Dendrimers with Farnesyl End-Groups ................................ 114
6.3.9 Diels-Alder Reaction on Dendrimer Periphery ..................... 116
6.4 Dendrimers with Silsesquioxane Core .............................................. 117
6.5 Conclusion......................................................................................... 118
Contents ix
7 Polyhedral Oligomeric Silsesquioxane Dendrimers.............................. 121
Katherine J. Haxton and Russell E. Morris
7.1 Introduction ....................................................................................... 121
7.2 Synthesis of Silsesquioxanes and Silicates ....................................... 123
7.2.1 Silsesquioxanes ..................................................................... 123
7.2.2 Silicates ................................................................................. 124
7.2.3 Functionalizing Silsesquioxanes and Silicates ...................... 125
7.3 Synthesis of POSS and Silicate Dendrimers ..................................... 126
7.3.1 POSS Dendrimer Synthesis................................................... 126
7.3.2 Silicate Dendrimer Synthesis ................................................ 129
7.3.3 Characterization .................................................................... 130
7.4 Applications of POSS and Silicate Dendrimers ................................ 130
7.4.1 Homogeneous Catalysis ........................................................ 130
7.4.2 Electro- and Redox-Active Dendrimers ................................ 133
7.4.3 Liquid Crystals ...................................................................... 133
7.4.4 Transition Metal Binding ...................................................... 134
7.4.5 POSS-PAMAM Nanocomposites ......................................... 135
7.4.6 Gene Transfection ................................................................. 136
7.5 Conclusion ........................................................................................ 137
8 Organometallic Silicon-Containing Dendrimers
and Their Electrochemical Applications ................................................ 141
Isabel Cuadrado
8.1 Introduction ....................................................................................... 141
8.2 Synthetic Strategies and Redox Properties
of Organometallic Silicon-Containing Dendritic
Macromolecules ................................................................................ 145
8.2.1 Functionalization of Silicon-Based Dendritic Scaffolds
with Electroactive Organometallic Moieties ......................... 147
8.2.2 Silicon-Based Dendrimers from Organometallic
Moieties ................................................................................. 163
8.3 Electrochemical Applications of Ferrocenyl Silicon-Containing
Dendritic Molecules .......................................................................... 183
8.3.1 Ferrocenyl Dendrimers with Si–NH Linkages
as Redox Sensors for Recognition of Inorganic Anions ....... 183
8.3.2 Ferrocenyl Silicon-Containing Dendrimers as
Electron-Transfer Mediators in Amperometric
Biosensors ............................................................................. 186
8.3.3 Electrocatalytic Oxidation of Ascorbic Acid Mediated
by a Ferrocenyl Siloxane-Based Network Polymer .............. 189
8.4 Concluding Remarks ......................................................................... 191
x Contents
9 Carbosilane Dendrimers: Molecular Supports
and Containers for Homogeneous Catalysis
and Organic Synthesis ........................................................................... 197
Maaike Wander, Robertus J.M. Klein Gebbink, and Gerard van Koten
9.1 Introduction ................................................................................... 197
9.2 Carbosilane Dendrimers with Covalently Bound Catalysts .......... 201
9.2.1 Synthesis and Structural Aspects
of Phosphine-Based Dendrimer Catalysts ....................... 201
9.2.2 Catalytic Reactivity of Phosphine-Based
Dendrimer Catalysts ........................................................ 203
9.2.3 Synthesis and Structural Aspects of
Non-phosphine-Based Dendrimer Catalysts ................... 213
9.2.4 Catalytic Reactivity of Non-phosphine-Based
Dendrimer Catalysts ........................................................ 214
9.3 Supported Organic Synthesis on Soluble Carbosilanes ................ 228
9.4 Conclusions and Future Outlook ................................................... 230
10 Liquid Crystalline Silicon-Containing Dendrimers
with Terminal Mesogenic Groups......................................................... 237
Valery Shibaev and Natalia Boiko
10.1 Introduction ................................................................................... 237
10.2 Peculiarities of the Molecular Structure
of LC Silicon-Containing Dendrimers .......................................... 240
10.3 Polyorganosiloxane Dendrimers with Terminal
Mesogenic Groups ........................................................................ 241
10.4 Carbosilane LC Dendrimers .......................................................... 246
10.4.1 Synthesis of Carbosilane LC Dendrimers
with Different Molecular Architectures .......................... 249
10.4.2 Structural Organization and Phase Behavior
of Carbosilane LC Dendrimers ....................................... 252
10.5 Chiral Carbosilane LC Dendrimers with Ferroelectric Properties 262
10.6 Photochromic LC Carbosilane Dendrimers .................................. 269
10.6.1 Phase Behavior and Structure ......................................... 272
10.6.2 Photochemical and Photooptical Properties .................... 274
10.7 Conclusions and Future Outlook ................................................... 279
11 Silicon-Organic Dendrimers ................................................................. 285
Petar R. Dvornic, Michael J. Owen, and Rakesh Sachdeva
11.1 Introduction ................................................................................... 285
11.2 PAMAMOS: PAMAM Dendrimers with Silicon-Containing
End-Groups ................................................................................... 287
11.3 PAMAMOS Multi-arm Star Polymers .......................................... 291
11.4 PAMAMOS Networks .................................................................. 294
11.5 PAMAMOS Networks Nanocomplexes and Nanocomposites ..... 298
11.6 Copolymeric PAMAMOS Dendrimers ......................................... 302