Dendrimers and dendrons : concepts, syntheses, applications / George R. Newkome, Charles N. Moorefield, Fritz Vögtle.

Format:

Book

Author/Creator:

Newkome, George R. (George Richard)

Contributor:

Moorefield, C. N. (Charles N.)

Vögtle, Fritz, 1939-2017.

Language:

English

Subjects (All):

Molecular structure.

Dendrimers.

Physical Description:

xii, 623 pages : illustrations ; 31 cm

Place of Publication:

Weinheim ; New York : Wiley-VCH, [2001]

Summary:

Having shaped this scientific field, the authors are able to brilliantly combine the basic principles with a wealth of more advanced information. The optimal presentation of the structural features of dendrimers helps readers to quickly understand even sophisticated syntheses. For special synthetic problems, the well-selected, detailed list of references allows easy access to further literature. This monograph will undoubtedly prove to be of interest for both beginners and advanced scientists in organic and pharmaceutical chemistry, as well as material science.

Contents:

1 Masses, Sizes, and Shapes of Macromolecules from Multifunctional Monomers

1.2 Molecular Mass and Chain Connectivity in Macromolecules 2

1.2.1 Distributions of Molecular Weight in Unbranched Chains 2

1.2.2 Branched Structures and Gelation with Multifunctional Monomers 3

1.2.3 Branching without Gelation 4

1.3 Overall Extension in Space: Molecular Sizes 5

1.3.1 Radius of Gyration 5

1.3.1.1 Unbranched Chains 6

1.3.1.2 Macrocycles 7

1.3.1.3 Branched Macromolecules 7

1.3.2 Breadth of the Distribution for the Squared Radius of Gyration 8

1.4 Shape Analysis from the Radius of Gyration Tensor 9

1.4.1 Principal Moments 10

1.4.2 Asphericity, Acylindricity, and Relative Shape Anisotropy 11

1.5 Approach to the Globular State by Unbranched Homopolymers 12

1.6 Simulations of the Conformations of Dendrimers 13

1.6.1 Mean Square Radius of Gyration 14

1.6.2 Shapes Deduced from the Radius of Gyration Tensor 15

1.6.3 Radial Distribution Functions: Hollow Core? 16

1.6.4 Locations of the Terminal Groups of the Last Generation 17

1.6.5 Stretching of the Spacers from Early Generations 17

1.6.6 Angular Segregation of Dendrons 17

1.6.7 Comments on Several Terms Used in the Description of Simulations 18

2 From Theory to Practice: Historical Perspectives, Self-Similarity, and Preparative Considerations

2.2 Branched Architectures 23

2.2.1 Early Observations 24

2.2.2 Prelude to Practice 25

2.2.3 Incipient Macromolecular Progression 27

2.2.3.2 Implied Dendritic Construction 27

2.2.3.3 Alternative Architectures 27

2.2.4 Accompanying Theoretical Framework 30

2.3 The Fractal Geometry of Macromolecules 33

2.3.2 Fractal Geometry 33

2.3.2.1 Self-similarity or Scale-invariance 34

2.3.2.2 Fractal Dimension (D) 34

2.3.3 Applied Fractal Geometry 34

2.3.3.1 Fractals in Chemistry 34

2.3.3.2 Fractals in Biology 36

2.3.3.3 Solvent Accessible Surface Area (A[subscript SAS]) 37

2.3.3.4 Dendritic Fractality 39

2.3.4 Fractal Summation 43

2.4 Dendritic Construction and Properties 43

2.4.1 Construction Methods 44

2.4.2 Monodispersity versus Unimolecular 45

3 Dendrimers Derived by Divergent Procedures Using 1 [right arrow] 2 Branching Motifs

3.2 Early Procedures 51

3.3 1 [right arrow] 2 Branched 55

3.3.1 1 [right arrow] 2 N-Branched and Connectivity 55

3.3.1.1 Surface Modifications 59

3.3.1.2 Dendron Attachment 64

3.3.1.3 Physical Properties 66

3.3.2 1 [right arrow] 2 N-Branched, Amide Connectivity 68

3.3.2.1 Surface Modifications 70

3.3.2.2 Physical Properties 76

3.3.2.3 Dendrimers as Attachments 81

3.3.3 1 [right arrow] 2 N-Branched, Aryl Connectivity 85

3.3.4 1 [right arrow] 2 N-Branched, Si-Connectivity 85

3.3.5 1 [right arrow] 2 N-Branched, N- & Amide-Connectivity 85

3.4 1 [right arrow] 2 Aryl-Branched 87

3.4.1 1 [right arrow] 2 Aryl-Branched, Amide Connectivity 87

3.4.2 1 [right arrow] 2 Aryl-Branched, Ester Connectivity 89

3.4.3 1 [right arrow] 2 Aryl-Branched, N-Connectivity 92

3.4.4 1 [right arrow] 2 Aryl-Branched, O-Connectivity 93

3.4.5 1 [right arrow] 2 Aryl & C-Branching and Connectivity 93

3.5 1 [right arrow] 2 C-Branched 99

3.5.1 1 [right arrow] 2 C-Branched, Amide Connectivity 99

3.5.2 1 [right arrow] 2 C-Branched and Connectivity 99

3.5.3 1 [right arrow] 2 C-Branched, Ether & Sulfone Connectivity 102

3.5.4 1 [right arrow] 2 C-Branched, Ether Connectivity 102

3.6 1 [right arrow] 2 Si-Branched and Connectivity 104

3.7 1 [right arrow] 2 P-Branched and Connectivity 113

4 Dendrimers Derived by Divergent Procedures Using 1 [right arrow] 3 Branching Motifs

4.1 1 [right arrow] 3 C-Branched, Amide Connectivity 141

4.1.1 1 [right arrow] 3 C-Branched, Amide ('Tris') Connectivity 141

4.1.2 1 [right arrow] 3 (1 [right arrow] 2) C-Branched, Amide ('Tris') Connectivity 146

4.1.3 1 [right arrow] 3 C-Branched, Amide ('Bishomotris') Connectivity 147

4.1.4 1 [right arrow] 3 C-Branched, Amide ("Behera's Amine") Connectivity 148

4.1.5 Physical Properties 158

4.2 1 [right arrow] 3 C-Branched and Connectivity 158

4.3 1 [right arrow] 3 C-Branched, Alkene & Ester Connectivity 160

4.4 1 [right arrow] 3 C-Branched, Ether Connectivity 161

4.5 1 [right arrow] 3 C-Branched, Ether & Amide Connectivity 164

4.6 1 [right arrow] 3 C-Branched, Ether, Amide, & Urea Connectivity 170

4.7 1 [right arrow] 3 C & 1 [right arrow] 2 N-Branched and Amide Connectivity 170

4.8 1 [right arrow] 3 N-Branched and Connectivity 170

4.9 1 [right arrow] 3 P-Branched and Connectivity 171

4.10 1 [right arrow] 3 Si-Branched and Connectivity 172

4.11 1 [right arrow] 3 Adamantane-Branched, Ester Connectivity 179

4.12 1 [right arrow] 4 N,C- (1 [right arrow] 2 N & 1 [right arrow] 2 C) Branched, Ether & Amide Connectivity 180

4.13 1 [right arrow] 5 N[subscript 3]P[subscript 3]-Branched, Alkyl Connectivity 180

5 Convergent Methodologies

5.2 1 arrow right 2 Branched 192

5.2.1 1 arrow right 2 C-Branched and Connectivity 192

5.2.2 1 arrow right 2 C-Branched, Alkyne Connectivity 194

5.2.3 1 arrow right 2 C-Branched, Ether Connectivity 195

5.2.4 1 arrow right 2 C-Branched, Ester Connectivity 205

5.2.5 1 arrow right 2 C-Branched, Ether & Imide Connectivity 206

5.3 1 arrow right 2 Aryl-Branched 206

5.3.1 1 arrow right 2 Aryl-Branched and Connectivity 206

5.3.2 1 arrow right 2 Aryl-Branched, Ether Connectivity 209

5.3.2.1 Focal Functionalization 212

5.3.2.2 Attachments 220

5.3.2.3 Terminal Modifications 234

5.3.2.4 Physical Properties 249

5.3.3 1 arrow right 2 Aryl-Branched, Amide Connectivity 250

5.3.4 1 arrow right 2 Aryl-Branched, Ammonium Connectivity 253

5.3.5 1 arrow right 2 Aryl-Branched & 1 arrow right 3 C-Branched, Ether & Amide Connectivity 253

5.3.6 1 arrow right 2 Aryl-Branched, Ether & Amide/Amine Connectivity 253

5.3.7 1 arrow right 2 Aryl-Branched, Ether & Urethane Connectivity 259

5.3.8 1 arrow right 2 Aryl-Branched, Ester Connectivity 259

5.3.9 1 arrow right 2 Aryl-Branched, Ether & Ester Connectivity 265

5.3.10 1 arrow right 2 Aryl-Branched, Ether and Ketone Connectivity 268

5.3.11 1 arrow right 2 Aryl-Branched, Alkyne Connectivity 268

5.3.12 1 arrow right 2 Aryl-Branched, Ethyne & Ester Connectivity 282

5.3.13 1 arrow right 2 Aryl-Branched, Oxadiazole Connectivity 285

5.3.14 1 arrow right 2 Aryl Branched, Alkene Connectivity 286

5.3.15 1 arrow right 2 Aryl Branched, Alkene & Ether Connectivity 288

5.4 1 arrow right 2 Pyridine-Branched, Ether Connectivity 289

5.5 1 arrow right 2 Other Heteroaryl-Branched and N-Connectivity 289

5.6 1 arrow right 2 N-Branched 292

5.6.1 1 arrow right 2 N-Branched, Amide Connectivity 292

5.6.2 1 arrow right 2 N-Branched, Amide & Azo Connectivity 292

5.6.3 1 arrow right 2 N-Branched, Ester & Azo Connectivity 295

5.6.4 1 arrow right 2 N-Branched and Connectivity 295

5.6.5 1 arrow right 2 N-Branched, Alkyne Connectivity 295

5.7 1 arrow right 2 C- & N-Branched, Ester Connectivity 295

5.8 1 arrow right 2 Si-Branched, Silyloxy Connectivity 298

5.9 1 arrow right 2 B-Branched, Aryl Connectivity 300

5.10 1 arrow right 2 TTF-Branched and Connectivity 300

5.11 1 arrow right 3 Aryl-Branched, Ether Connectivity 300

5.12 1 arrow right 3 C-Branched, Amide Connectivity 304

5.13 1 arrow right 3 C-Branched, Ether & Amide Connectivity 306

5.14 1 arrow right 3(2) Silatrane-Branched, Amine Connectivity 306

5.15 1 arrow right 4 Amine and Aryl Branched, Amide Connectivity 310

6 Hyperbranched Materials

6.2 1 arrow right 2 Aryl-Branched 332

6.2.1 1 arrow right 2 Aryl-Branched and Connectivity 332

6.2.2 1 arrow right 2 Aryl-Branched, Ester Connectivity 334

6.2.3 1 arrow right 2 Aryl-Branched, Ether Connectivity 338

6.2.4 1 arrow right 2 Aryl-Branched, Amine Connectivity 342

6.2.5 1 arrow right 2 Aryl-Branched, Ether & Ketone Connectivity 342

6.2.6 1 arrow right 2 Aryl-Branched, Amide

Connectivity 346

6.2.7 1 arrow right 2 Aryl-Branched, Urethane Connectivity 349

6.2.8 1 arrow right 2 Aryl-Branched, Urea Connectivity 350

6.2.9 1 arrow right 2 Aryl-Branched, Ether & Ester Connectivity 350

6.2.10 1 arrow right 2(3) Aryl-Branched, Amide & Ester Connectivity 350

6.2.11 1 arrow right 2 Aryl-Branched, Ether & Ester Connectivity 352

6.2.12 1 arrow right 2 Aryl-Branched, S-Connectivity 352

6.2.13 1 arrow right 2 Aryl-Branched, C-Connectivity 353

6.2.14 1 arrow right 2 Aryl-Branched, Alkyne Connectivity 353

6.2.15 1 arrow right 2 Aryl-Branched, Alkene Connectivity 355

6.2.16 1 arrow right 2 Aryl-Branched, Imide & Ether Connectivity 355

6.3 1 arrow right 2 Heteroaryl-Branched 356

6.3.1 1 arrow right 2 Heteroaryl-Branched, Ether Connectivity 356

6.3.2 1 arrow right 2 Heteroaryl-Branched, Ethyne and Ether Connectivity 357

6.4 1 arrow right 2 C-Branched 357

6.4.1 1 arrow right 2 C-Branched, Ester Connectivity 357

6.4.2 1 arrow right 2 C-Branched, Ether Connectivity 366

6.4.3 1 arrow right 2 C-Branched, Amide Connectivity 370

6.4.4 1 arrow right 2 C-Branched, Alkane Connectivity 370

6.4.5 1 arrow right 2 C-Branched, Carbonate Connectivity 371

6.4.6 1 arrow right 2 C-Branched, Ether & Ester Connectivity 372

6.5 1 arrow right 2 N-Branched 372

6.5.1 1 arrow right 2 N-Branched and Connectivity 372

6.5.2 1 arrow right 2 N-Branched, Amide Connectivity 372

6.5.3 1 arrow right 2 N-Branched and Connectivity 373

6.5.4 1 arrow right 2 N-Branched, Aryl Connectivity 373

6.6 1 arrow right 3 C-Branched, Ester Connectivity 375

6.7 1 arrow right 3 C-Branched, Ether Connectivity 375

6.8 1 arrow right 3 Ge-Branched and Connectivity 375

6.9 1 arrow right 3(2) Si-Branched and Connectivity 377

6.10 1 arrow right 3 Cyclotetraveratrylene-Branched, Ether Connectivity 379

6.11 1 arrow right 3 Aryl-Branched, Ester Connectivity 380

6.12 1 arrow right 2 Heteroaromatic Branched 381

7 Chiral Dendritic Macromolecules

7.1 Divergently Generated Chiral Dendrimers 395

7.1.1 1 arrow right 2 Branched 395

7.1.1.1 1 arrow right 2 C-Branched, Amide Connectivity 395

7.1.1.2 1 arrow right 2 C-Branched, Amide & Ester Connectivity 402

7.1.1.3 1 arrow right 2 N-Branched & Connectivity 402

7.1.1.4 1 arrow right 2 N-Branched, Amide Connectivity 406

7.1.1.5 1 arrow right 2 N- & 1 arrow right 3 C-Branched, Amide Connectivity 412

7.1.1.6 1 arrow right 2 Aryl-Branched, Ether Connectivity 412

7.1.1.7 1 arrow right 2 Aryl-Branched, Ester & Amide Connectivity 413

7.1.1.8 1 arrow right 2 Aryl-Branched, Ether & Ester Connectivity 413

7.1.1.9 1 arrow right 2 Aryl-Branched, Ether & Amide Connectivity 414

7.1.1.10 1 arrow right 2 Ethano-Branched, Ether Connectivity 414

7.1.2 1 arrow right 3 Branched 415

7.1.2.1 1 arrow right 3 C-Branched, Ether & Amide Connectivity 415

7.1.2.2 1 arrow right 3 C-Branched, Ether Connectivity 416

7.1.2.3 1 arrow right 3 Aryl-Branched, Ether & Amide Connectivity 417

7.1.2.4 1 arrow right 3 Si-Branched, Thio & Alkyl Connectivity 417

7.1.2.5 1 arrow right 3 P-Branched and Phosphate Connectivity 417

7.2 Convergently Generated Chiral Dendrimers 419

7.2.1 1 arrow right 2 Branched 419

7.2.1.1 1 arrow right 2 C-Branched, Amide Connectivity 419

7.2.1.2 1 arrow right 2 Aryl-Branched, Ether Connectivity 420

7.2.1.3 1 arrow right 2 Aryl-Branched, Ester Connectivity 431

7.2.1.4 1 arrow right 2 Aryl-Branched, Amide Connectivity 431

7.2.1.5 1 arrow right 2 Aryl-Branched, Alkyne Connectivity 431

7.2.1.6 1 arrow right 2 Ethano-Branched, Phosphate Connectivity 432

7.2.1.7 1 arrow right 2 N-, 1 arrow right 3 C-Branched Amide Connectivity 435

7.2.1.8 1 arrow right 2 & 3 C-Branched Amide & Thiourea (& Ether) Connectivity 440

7.2.1.9 1 arrow right 2-Saccharide-Branched, Ether & Amine Connectivity 440

7.2.2 1 arrow right 3 Branched 440

7.2.2.1 1 arrow right 3 C-Branched, Amide Connectivity 440

7.2.2.2 1 arrow right 3 P- & Aryl-Branched, P- & Ether Connectivity 441

7.2.2.3 1 arrow right 3(2) Cholic Acid-Branched, Ester Connectivity 443

7.2.2.4 1 arrow right 3 Aryl-Branched, Amide & Ether Connectivity 443

7.3 Hyperbranched Derived Motifs 444

7.3.1 Saccharide-Branched, Ether-Connectivity 444

8 Metallodendrimers

8.2 Metals as Branching Centers 457

8.3 Metals as Building Block Connectors 462

8.4 Metals as Cores 472

8.5 Metals as Termination Groups (Surface Functionalization) 488

8.6 Metals as Structural Auxiliaries 510

8.6.1 Site-Specific Inclusion 510

8.6.2 Random Metal Inclusion 514

9 Dendritic Networks

9.1 Introduction: Dendritic Assemblies 539

9.2 Network Formation and Classification 540

9.2.1 Ordered versus Random 540

9.2.1.1 Methods of Formation 541

9.2.1.2 Covalent and Non-Covalent Positioning 542

9.3 Random Connectivity 542

9.3.1 Random, Covalently-Linked Dendrimer Networks 542

9.3.2 Coupling through Surface-to-Surface Interaction 543

9.3.3 Coupling via Surface-to-Surface Bridging Units 544

9.3.4 Random, Non-Covalent 545

9.4 Ordered Dendritic Networks 545

9.4.1 Multilayer Construction 545

9.4.2 Directed Network Construction 547

9.4.2.1 Covalent, Metal-Based Assembly 547

9.4.2.2 Hyperbranched-Type, Metal-Based Assembly 548

9.4.2.3 Hydrogen-Bonding Assembly 550

9.4.2.4 Covalent Assembly 553

9.4.2.5 Charge-Induced Self-Assembly 557

10.1 Key Reviews and Highlights Covering Dendrimers and Hyperbranched Materials 563

10.1.1 2001 Reviews 563

10.1.1 2000 Reviews 564

10.1.2 2000 Reviews 564

10.1.2 1999 Reviews 565

10.1.3 1998 Reviews 566

10.1.4 1997 Reviews 567

10.1.5 1996 Reviews 568

10.1.6 1995 Reviews 569

10.1.7 1994 Reviews 570

10.1.8 1993 Reviews 571

10.1.9 1992 Reviews 572

10.1.10 1991 and Earlier Reviews 572

10.2 Advances Series 573

10.3 SEARCH Series 575

10.4 Topics in Current Chemistry 575

10.5 Other Reviews that Directly Impact Dendritic and Hyperbranched Chemistry 576

10.6.1 Background on Trivial and Traditional Names 581

10.6.2 Definition of a Cascade Polymer 582

10.6.3 Proposed Cascade Nomenclature Rules[superscript [12, 13] 582

10.6.4 General Patterns 583

10.6.4.1 Similar Repeat Internal Units 583

10.6.4.2 Similar Arms with Dissimilar Internal Units 585

10.6.4.3 Dissimilar Arms with Similar Internal Branches 585

10.6.4.4 Dissimilar Arms with Dissimilar Internal Branches or Terminal Groups 587

10.6.4.5 Unsymmetrically Branched Cascades 587

10.6.5 Fractal Notation 587

10.6.5.1 General Rules for the Proposed Fractal Notation 590

10.6.5.2 Examples Using the Fractal Rules 590.

Notes:

Includes bibliographical references and index.

ISBN:

3527299971

OCLC:

46601245