Terpyridine-based materials : for catalytic, optoelectronic and life science applications

In recent years, the utilization of terpyridines both in macromolecular structure assembly and device chemistry has exploded, enabling, for
example, supramolecular polymer architectures with switchable chemical and physical properties as well as novel functional materials
for optoelectronic applications such as light-emitting diodes and solar cells. Further applications include the usage of terpyridines and their
metal complexes as catalysts for asymmetric organic reactions and, in a biological context, as anti-tumor agents or biolabels. This book covers terpyridine-based materials topics ranging from syntheses, chemistry, and multinuclear metal complexes, right up to functionalized polymers, 3D-architectures, and surfaces. Aimed at materials scientists, (in)organic chemists, polymer chemists, complex chemists, physical chemists, biochemists, and libraries.

Author Notes

Ulrich S. Schubert performed his Ph.D. work under the supervision of Prof. C. D. Eisenbach (Bayreuth, Germany) and Prof. C. R. Newkome (Florida, USA). After a postdoctoral training with Prof.J.M. Lehn at the University Strasbourg (France), he moved to the Munich University of Technology (Germany) to obtain his habilitation in 1999. From 1999 to spring 2000, he held a temporary position as a professor at the Center for NanoScience at the LMU Munich. From June 2000 to March 2007, he was Full-Professor at the Eindhoven University of Technology (Chair for Macromolecular Chemistry and Nanoscience), the Netherlands. Since April 2007, he is Full Professor at the Friedrich-Schiller-University Jena (Chair of Organic and Macromolecular Chemistry), Germany. He has published over 500 papers, 18 patents, and edited/written 5 scientific books.
Andreas Winter studied chemistry at the University of Dortmund (Germany), where he graduated in organic chemistry in 1999. In 2003, he received his Ph.D. in chemistry (University of Paderborn, Germany) for work on applications of the Mannich reaction in the synthesis of pyridine derivatives under supervision of Professor N. Risch, and stayed on as a postdoc. Subsequently, in 2005 he joined the group of Prof. U. S. Schubert (Eindhoven University of Technology, The Netherlands and Friedrich Schiller University Jena, Germany). His research is focused on the synthesis of emissive and luminescent metallo-supramolecular assemblies.
George R. Newkome received his B.S. and Ph.D. in chemistry from Kent State University. He became a full professor in 7978 and Distinguished Research Master in 1982 at Louisiana State University, In 1986, he moved to the University of South Florida as Vice President for Research and Professor of Chemistry, becoming a Distinguished Research Professor in 1992. In 2001, he became Vice President for Research and Dean of the Graduate School at The University of Akron. He is the Oelschlager Professor of Science and Technology and professor in the departments of Polymer Science and Chemistry. Currently, he is the President and CEO of the University of Akron's Research Foundation and the Akron Innovation Campus. He has published over 430 papers, 45 patents, and edited/written over 15 scientific books and monographs.

Ion Complexes

Preface	p. ix
List of Abbreviations	p. xi
1 Introduction	p. 1
2 Synthesis, Properties, and Applications of Functionalized 2,2':6',2"-Terpyridines	p. 13
2.1 Introduction	p. 13
2.2 Basic Synthetic Strategies	p. 13
2.2.1 Ring Assembly Methodologies	p. 14
2.2.2 Cross Coupling Procedures	p. 18
2.3 Synthesis and Properties of 2,2':6',2"-Terpyridine Derivatives	p. 19
2.3.1 4'-Substituted 2,2':6',2"-Terpyridinoxy Derivatives	p. 19
2.3.2 Miscellaneous 4'-Substituted 2,2':6',2"-Terpyridine Derivatives	p. 24
2.4 2,2':6',2"-Terpyridines Symmetrically Substituted on the Outer Pyridine Rings	p. 28
2.5 Ziessel Type 2,2':6',2"-Terpyridines	p. 31
2.6 Krohnke Type 2,2':6',2"-Terpyridines	p. 38
2.7 Miscellaneous Terpyridine-Analogous Compounds	p. 49
2.7.1 Rigid U and S Shaped Terpyridines	p. 49
2.7.2 Five Membered N-Heterocycles Replacing the Outer Pyridine Rings	p. 51
2.7.3 The Swedish Concept: Expanded Bite Angles in Tridentate Ligands	p. 53
3 Chemistry and Properties of Terpyridine Transition Metal	p. 65
3.1 Introduction	p. 65
3.2 Basic Synthetic Strategies and Characterization Tools	p. 66
3.3 Ru11 and Os11 Complexes	p. 73
3.3.1 Synthesis of Ru11 and Os11 Bis(terpyridine) Complexes	p. 73
3.3.2 Ru11 Ions and Terpyridine Ligands-A Happy Marriage?	p. 75
3.3.2.1 Photophysical Properties	p. 75
3.3.2.2 Mononuclear Ru Bis(terpyridine) Complexes	p. 76
3.3.2.3 Oligonuclear Complexes Containing Ru/Os11 Bis(terpyridine) Units	p. 89
3.3.2.4 Dendritic and Star-Shaped Systems Containing Ru11 Bis(terpyridine) Units	p. 102
3.4 Iridium (III) Complexes with Terpyridine Iigands	p. 107
3.5 Platinum(II) Mono(terpyridine) Complexes	p. 115
4 Metallo Supramolecular Architectures Based on Terpyridine Complexes	p. 129
4.1 Introduction	p. 129
4.2 Terpyridme Containing Metallo Macrocycles	p. 130
4.3 The HETTAP Concept	p. 148
4.4 Racks and Grids	p. 154
4.5 Helicates	p. 171
4.6 Rotaxanes and Catenanes	p. 177
4.7 Miscellaneous Structures	p. 182
4.7.1 Cyclodextrin Derivatives	p. 182
4.7.2 Other Assemblies	p. 185
5 ¿-Conjugated Polymers Incorporating Terpyridine Metal Complexes	p. 199
5.1 Introduction	p. 199
5.2 Metallo Supramolecular Polymerization	p. 200
5.3 Metallopolymers Based on Conjugated Bis(terpyridine)s	p. 204
5.3.1 Polymerization by Transition Metal Ion Coordination	p. 204
5.3.2 Self Assembly of Metallopolymers	p. 212
5.3.3 Chiral Metallopolymers	p. 219
5.3.4 Non Classical Metallopolymers	p. 220
5.3.5 Polymerization Using the "Complex First" Method	p. 224
5.4 Main Chain Metallopolymers Based on Terpyridine Functionalized ¿-Conjugated Polymers	p. 229
6 Functional Polymers Incorporating Terpyridine-Metal Complexes	p. 242
6.1 Introduction	p. 242
6.2 Polymers with Terpyridine Units in the Side Chain	p. 242
6.2.1 Materials Based on Flexible Organic Polymers	p. 242
6.2.2 Materials Based on Conjugated Polymers	p. 257
6.3 Polymers with Terpyridines within the Polymer Backbone	p. 262
6.3.1 Polymers from Organic Small-Molecule Building Blocks	p. 263
6.3.2 Chain-Extended Polymers from Polymeric Building Blocks	p. 269
6.3.3 Monotopic Macroligands by End Group Funtionalization	p. 272
6.3.4 Functional Terpyridine Containing Initiators	p. 277
6.3.4.1 Initiation of Ionic Polymerization Reactions	p. 277
6.3.4.2 Initiation of Controlled Radical Polymerization Reactions	p. 281
6.3.4.3 Post Polymerization Functionalization	p. 288
6.3.5 Mononuclear Metallo-supramolecular Polymers	p. 291
6.3.5.1 Supramolecular A-[M]-A Homopolymers	p. 291
6.3.5.2 Supramolecular Block Copolymers	p. 294
6.3.6 Oligonuclear Metallo Supramolecular Copolymers	p. 308
7 Terpyridine Metal Complexes and their Biomedical Relevance	p. 319
7.1 Introduction	p. 319
7.2 Terpyridine Metal Complexes with Biological Activity	p. 320
7.2.1 Intercalation and Cytotoxicity	p. 320
7.2.1.1 Terpyridine Complexes with d 8 Late Transition Metal Ions	p. 320
7.2.1.2 Terpyridine Complexes with Heavy d 6 Transition Metal Ions	p. 350
7.2.1.3 Terpyridine Complexes with MisceEaneous Transition Metal Ions	p. 364
7.2.2 Biolabeling	p. 376
8 Terpyridines and Nanostructures	p. 399
8.1 Introduction	p. 399
8.2 Terpyridines and Surface Chemistry	p. 401
8.3 Terpyridines and Inorganic Nanomaterials	p. 420
8.4 Terpyridines and Nano Structured TiO 2 : Photovoltaic Applications	p. 431
8.5 Organopolymeric Resins, Beads, and Nanoparticles	p. 447
9 Catalytic Applications of Terpyridines and Their Transition Metal Complexes	p. 459
9.1 Introduction	p. 459
9.2 Asymmetric Catalysts in Organic Reactions	p. 460
9.3 Electrocatalytic Oxidation and Reduction Processes	p. 476
9.4 Photocatalytic Processes	p. 480
9.4.1 Light-Driven Hydrogen Formation	p. 483
9.4.2 Molecular Terpyridine Based Catalysts for Water Oxidation	p. 488
10 Concluding Remarks	p. 507
Index	p. 509

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Author Notes

Table of Contents