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Silicon-Containing Dendritic Polymers

:	Petar R. Dvornic, Michael J. Owen
:	Petar R. Dvornic, Michael J Owen
:	Silicon-Containing Dendritic Polymers
:	Springer-Verlag
:	9781402081743
:	1
:	CHF 132.90
:

:	Organische Chemie
:	English

:	428
:	Wasserzeichen
:	PC/MAC/eReader/Tablet
:	PDF

During the last two decades silicon-containing dendritic polymers have become one of the fastest growing areas of development in polymer science. The eruption of interest in these new polymers stems from their unprecedented molecular architecture, unique resulting properties and the realization that they represent ideal building blocks for chemical nanotechnology.

This is the first book to solely focus on silicon-containing dendritic polymers. The contributions of those experts who originally introduced each field or played a major role in its progress are reported. The developments in all major areas of this field are presented from their origins to the present. It is anticipated that this text will become an invaluable guide and vanguard of reference for experienced scientists interested in the fields of polymer and material science, synthetic chemistry, and nanotechnology. It will also serve advanced graduate students either as a source of creative inspiration or as a textbook for appropriate courses.

	Preface	6
	Contents	8
	Contributors	14
	The Role of Silicon in Dendritic Polymer Chemistry	17
	1.1 Introduction	17
	1.2 Dendrimers and Hyperbranched Polymers	20
	1.2.1 Dendrimers	20
	1.2.2 Hyperbranched Polymers	26
	1.3 A Brief Historical Overview of the Main Developments in Dendrimers and Hyperbranched Polymers	29
	1.4 Silicon in Dendritic Polymers	31
	References	34
	Polysiloxane and Siloxane-Based Dendrimers	37
	2.1 Introduction: Historical Background	37
	2.2 Chemistry of Siloxane Dendrimers	38
	2.3 Peculiarities of Siloxane Dendrimers	41
	2.4 Prospects for Further Development in the Chemistry of Siloxane Dendrimers	44
	References	45
	Carbosilane Dendrimers	47
	3.1 Introduction	47
	3.2 Synthesis of Carbosilane Dendrimers	48
	3.2.1 Core Molecules	49
	3.2.2 Interior Generations	54
	3.2.3 Peripheral (Corona	End-Groups) Modification
	3.3 Carbosilane Dendrimer Characterization	76
	3.4 Properties of Carbosilane Dendrimers	78
	3.4.1 Molecular Dimensions of Carbosilane Dendrimers	78
	3.4.2 Dynamics of Carbosilane Dendrimers	82
	References	84
	Polysilane Dendrimers	91
	4.1 Introduction	91
	4.2 Synthetic Approaches to Polysilane Dendrimers	92
	4.2.1 Convergent Methods	92
	4.2.2 Divergent Methods	95
	4.2.3 Double-Cored Polysilane Dendrimers	97
	4.2.4 Functionalized Polysilane Dendrimers	100
	4.3 NMR Spectroscopy of Polysilane Dendrimers	101
	4.4 Crystallography and Conformation of Polysilane Dendrimers	103
	4.5 Electronic Spectra	107
	4.6 Conclusions and Future Outlook	110
	References	111
	Polycarbosilazane and Related Dendrimers and Hyperbranched Polymers	113
	5.1 Introduction	113
	5.2 Polycarbosilazane Dendrimers	114
	5.3 Polysilazane Dendrimers	115
	5.4 Related Dendrimers	116
	5.5 Hyperbranched Polycarbosilazanes	117
	5.6 Concluding Remarks	118
	References	119
	Silyl Ether Containing Dendrimers with Cyclic Siloxane Cores	120
	6.1 Introduction	120
	6.2 Siloxane Dendrimers with Cyclic Siloxane Core ( 0G( 4)- Vinyl)	121
	6.3 Synthesis of Dendrimers with Si–O–C Units from Cyclic Siloxane Cores	123
	6.3.1 General Synthetic Strategy from 0G(4)-Vinyl Core	123
	6.3.2 Dendrimers with Organic Functional End-Groups	123
	6.3.3 Dendrimers with Triple Bonds	124
	6.3.4 “Double-Layered” Dendrimers with Conjugated Branches	125
	6.3.5 Ferrocenyl-Functionalized Dendrimers as CO Gas Sensor	127
	6.3.6 Water Soluble Dendrimers	127
	6.3.7 Dendrimers with Terpyridine Ruthenium Complex End- Groups	129
	6.3.8 Dendrimers with Farnesyl End-Groups	129
	6.3.9 Diels-Alder Reaction on Dendrimer Periphery	131
	6.4 Dendrimers with Silsesquioxane Core	132
	6.5 Conclusion	133
	References	133
	Polyhedral Oligomeric Silsesquioxane Dendrimers	135
	7.1 Introduction	135
	7.2 Synthesis of Silsesquioxanes and Silicates	137
	7.2.1 Silsesquioxanes	137
	7.2.2 Silicates	138
	7.2.3 Functionalizing Silsesquioxanes and Silicates	139
	7.3 Synthesis of POSS and Silicate Dendrimers	140
	7.3.1 POSS Dendrimer Synthesis	140
	7.3.2 Silicate Dendrimer Synthesis	143
	7.3.3 Characterization	144
	7.4 Applications of POSS and Silicate Dendrimers	144
	7.4.1 Homogeneous Catalysis	144
	7.4.2 Electro- and Redox-Active Dendrimers	147
	7.4.3 Liquid Crystals	147
	7.4.4 Transition Metal Binding	148
	7.4.5 POSS-PAMAM Nanocomposites	149
	7.4.6 Gene Transfection	150
	7.5 Conclusion	151
	References	151
	Organometallic Silicon-Containing Dendrimers and Their Electrochemical Applications	154
	8.1 Introduction	154
	8.2 Synthetic Strategies and Redox Properties of Organometallic Silicon- Containing Dendritic Macromolecules	158
	8.2.1 Functionalization of Silicon-Based Dendritic Scaffolds with Electroactive Organometallic Moieties	160
	8.2.2 Silicon-Based Dendrimers from Organometallic Moieties	176
	8.3 Electrochemical Applications of Ferrocenyl Silicon- Containing Dendritic Molecules	196
	8.3.1 Ferrocenyl Dendrimers with Si–NH Linkages as Redox Sensors for Recognition of Inorganic Anions	196
	8.3.2 Ferrocenyl Silicon-Containing Dendrimers as Electron- Transfer Mediators in Amperometric Biosensors	199
	8.3.3 Electrocatalytic Oxidation of Ascorbic Acid Mediated by a Ferrocenyl Siloxane- Based Network Polymer	202
	8.4 Concluding Remarks	204
	References	205
	Carbosilane Dendrimers: Molecular Supports and Containers for Homogeneous Catalysis and Organic Synthesis	210
	9.1 Introduction	210
	9.2 Carbosilane Dendrimers with Covalently Bound Catalysts	214
	9.2.1 Synthesis and Structural Aspects of Phosphine-Based Dendrimer Catalysts	214
	9.2.2 Catalytic Reactivity of Phosphine-Based Dendrimer Catalysts	216
	9.2.3 Synthesis and Structural Aspects of Non-phosphine-Based Dendrimer Catalysts	226
	9.2.4 Catalytic Reactivity of Non-phosphine-Based Dendrimer Catalysts	227
	9.3 Supported Organic Synthesis on Soluble Carbosilanes	241
	9.4 Conclusions and Future Outlook	243
	References	245
	Liquid Crystalline Silicon-Containing Dendrimers with Terminal Mesogenic Groups	249
	10.1 Introduction	249
	10.2 Peculiarities of the Molecular Structure of LC Silicon- Containing Dendrimers	252
	10.3 Polyorganosiloxane Dendrimers with Terminal Mesogenic Groups	253
	10.4 Carbosilane LC Dendrimers	258
	10.4.1 Synthesis of Carbosilane LC Dendrimers with Different Molecular Architectures	261