Main Group Strategies towards Functional Hybrid Materials

Dr. rer. nat. Thomas Baumgartner, is a Professor and Canada Research Chair in the Department of Chemistry, York University, Canada. He is the recipient of several awards, including a Liebig fellowship from the German chemical industry association, an Alberta Ingenuity New Faculty Award, a JSPS invitation fellowship, and a Friedrich Wilhelm Bessel Research Award from the Alexander von Humboldt Foundation. Dr. rer. nat. Frieder Jäkle, is a Distinguished Professor in the Department of Chemistry, Rutgers University-Newark, USA. He is the recipient of the NSF CAREER award, an Alfred P. Sloan fellowship, a Friedrich Wilhelm Bessel Research Award from the Alexander von Humboldt foundation, the ACS Akron Section Award, and the Boron Americas Award.

• List of Contributors xvPreface xix1 Incorporation of Boron into π-Conjugated Scaffolds to Produce Electron-Accepting π-Electron Systems 1Atsushi Wakamiya1.1 Introduction 11.2 Boron-Containing Five-Membered Rings: Boroles and Dibenzoboroles 21.3 Annulated Boroles 81.4 Boron-Containing Seven-Membered Rings: Borepins 111.5 Boron-Containing Six-Membered Rings: Diborins 141.6 Planarized Triphenylboranes and Boron-Doped Nanographenes 171.7 Conclusion and Outlook 21References 222 Organoborane Donor–Acceptor Materials 27Sanjoy Mukherjee and Pakkirisamy Thilagar2.1 Organoboranes: Form and Functions 272.2 Linear D-A Systems 292.3 Non-conjugated D-A Organoboranes 322.4 Conjugated Nonlinear D-A Systems 332.5 Polymeric Systems 362.6 Cyclic D-A Systems: Macrocycles and Fused-Rings 392.7 Conclusions and Outlook 43References 433 Photoresponsive Organoboron Systems 47Soren K. Mellerup and Suning Wang3.1 Introduction 473.1.1 Four-Coordinate Organoboron Compounds for OLEDs 473.1.2 Photochromism 493.2 Photoreactivity of (ppy)BMes2 and Related Compounds 503.2.1 Photochromism of (ppy)BMes2 503.2.2 Mechanism 513.2.3 Derivatizing (ppy)BMes2: Impact of Steric and Electronic Factors on Photochromism 523.2.3.1 Substituents on the ppy Backbone 523.2.3.2 Aryl Groups on Boron: Steric versus Electronic Effect 543.2.3.3 π-Conjugation and Heterocyclic Backbones 563.2.3.4 Impact of Different Donors 583.2.3.5 Polyboryl Species 603.3 Photoreactivity of BN-Heterocycles 623.3.1 BN-Isosterism and BN-Doped Polycyclic Aromatic Hydrocarbons (PAHs) 623.3.2 Photoelimination of (2-Benzylpyridyl)BMes2 623.3.3 Mechanism 643.3.4 Scope of Photoelimination: The Chelate Backbone 653.3.5 Strategies of Enhancing ΦPE: Metalation and Substituents on Boron 663.4 New Photochromism of BN-Heterocycles 683.4.1 Photochromism of (2-Benzylpyridyl)BMesF 2 and Related Compounds 683.4.2 Mechanism 703.5 Exciton Driven Elimination (EDE): In situ Fabrication of OLEDs 703.6 Summary and Future Prospects 73References 744 Incorporation of Group 13 Elements into Polymers 79Yi Ren and Frieder Jäkle4.1 Introduction 794.2 Tricoordinate Boron in Conjugated Polymers 804.3 Tetracoordinate Boron Chelate Complexes in Polymeric Materials 874.3.1 N-N Boron Chelates 884.3.2 N-O Boron Chelates 914.3.3 N-C Boron Chelates 924.4 Polymeric Materials with B-P and B-N in the Backbone 924.5 Polymeric Materials Containing Borane and Carborane Clusters 974.6 Polymeric Materials Containing Higher Group 13 Elements 1014.7 Conclusions 105Acknowledgements 106References 1065 Tetracoordinate Boron Materials for Biological Imaging 111Christopher A. DeRosa and Cassandra L. Fraser5.1 Introduction 1115.1.1 Introduction to Luminescence 1115.1.2 Tetracoordinate Boron Dye Scaffolds 1135.2 Small Molecule Fluorescence Imaging Agents 1145.2.1 Bright Fluorophores 1165.2.2 Solvatochromophores 1175.2.3 Molecular Motions of Boron Dyes 1185.2.3.1 Molecular Rotors 1215.2.3.2 Turn-On Probes 1215.3 Polymer Conjugated Materials 1245.3.1 Dye–Polymer Systems 1245.3.2 Oxygen-Sensing Polymers 1265.3.3 Energy Transfer in Polymers 1295.3.4 Conjugated Polymers 1305.3.5 Aggregation-Induced Emission Polymers 1305.4 Conclusion and Future Outlook 133References 1336 Advances and Properties of Silanol-Based Materials 141Rudolf Pietschnig6.1 Introduction 1416.2 Preparation 1416.3 Reactivity 1436.3.1 Adduct Formation 1436.3.2 Metallation 1456.3.3 Condensation 1466.4 Properties and Application 1486.4.1 Surface Modification 1486.4.2 Catalysis 1546.4.3 Bioactivity 1556.4.3.1 Monosilanols 1556.4.3.2 Silanediols 1566.4.3.3 Silanetriols 1576.4.4 Supramolecular Assembly 158References 1597 Silole-Based Materials in Optoelectronics and Sensing 163Masaki Shimizu7.1 Introduction 1637.2 Basic Aspects of Silole-Based Materials 1647.3 Silole-Based Electron-Transporting Materials 1677.4 Silole-Based Host and Hole-Blocking Materials for OLEDs 1707.5 Silole-Based Light-Emitting Materials 1717.6 Silole-Based Semiconducting Materials 1757.7 Silole-Based Light-Harvesting Materials for Solar Cells 1797.8 Silole-Based Sensing Materials 1857.9 Conclusion 189References 1908 Materials Containing Homocatenated Polysilanes 197Takanobu Sanji8.1 Introduction 1978.2 Synthesis 1978.3 Functional Modification of Polysilanes 1988.4 Control of the Stereochemistry of Polysilanes 1998.5 Control of the Secondary Structure of Polysilanes 2008.6 Polysilanes with 3D Architectures 2028.7 Applications 2038.8 Summary 205References 2059 Catenated Germanium and Tin Oligomers and Polymers 209Daniel Foucher9.1 Introduction 2099.2 Oligogermanes and Oligostannanes 2099.3 Preparation of Polygermanes 2129.3.1 Wurtz Coupling 2129.3.2 Reductive coupling of Dihalogermylenes 2149.3.3 Electrochemical Reduction of Dihalodiorganogermanes and Trihaloorganogermanes 2159.3.4 Transition Metal-Catalyzed Polymerizations of Germanes 2159.3.4.1 Demethanative Coupling of Germanes 2169.3.5 Photodecomposition of Germanes 2189.3.6 Properties and Characterization of Polygermanes 2189.3.6.1 Thermal Properties of Polygermanes 2189.3.6.2 Electronic Properties of Polygermanes 2199.4 Preparation of Polystannanes 2209.4.1 Wurtz Coupling 2209.4.2 Electrochemical Synthesis 2219.4.3 Dehydropolymerization 2249.4.4 Alternating Polystannanes 2279.4.5 Properties and Characterization of Polystannanes 2279.4.5.1 Sn NMR 2279.4.5.2 Thermal and Photostability 2289.4.5.3 Electronic Properties 2309.4.5.4 Conductivity 2319.4.6 Molecular Modeling of Oligostannanes and Comparison of Group 14 Polymetallanes 2319.5 Conclusions and Outlook 233Acknowledgements 233References 23410 Germanium and Tin in Conjugated Organic Materials 237Yohei Adachi and Joji Ohshita10.1 Introduction 23710.2 Germanium and Tin-Linked Conjugated Polymers 23810.2.1 Germylene-Ethynylene Polymers 23810.2.2 Fluorene- and Carbazole-Containing Germylene Polymers 24010.2.3 Germanium- and Tin-Linked Ferrocenes and Related Compounds 24110.3 Germanium- and Tin-Containing Conjugated Cyclic Systems 24210.3.1 Non-fused Germoles and Stannoles 24210.3.2 Dibenzogermoles and Dibenzostannoles 24810.3.3 Dithienogermole and Dithienostannole 25310.3.4 Other Fused Germoles 25810.3.5 Germacycloheptatriene and Digermacyclohexadiene 25910.4 Summary and Outlook 260References 26011 Phosphorus-Based Porphyrins 265Yoshihiro Matano11.1 Introduction 26511.2 Porphyrins Bearing Phosphorus-Based Functional Groups at their Periphery 26611.2.1 Porphyrins Bearing meso/β-Diphenylphosphino Groups 26611.2.2 Porphyrins Bearing meso/β-Triphenylphosphonio Groups 26911.2.3 Porphyrins Bearing meso/β-Diphenylphosphoryl Groups 27311.2.4 Porphyrins Bearing meso/β-Dialkoxyphosphoryl Groups 27611.2.5 Phthalocyanines Bearing Phosphorus-Based Functional Groups 28011.3 Porphyrins and Related Macrocycles Containing Phosphorus Atoms at their Core 28311.3.1 Core-Modified Phosphaporphyrins 28411.3.2 Core-Modified Phosphacalixpyrroles 28711.3.3 Core-Modified Phosphacalixphyrins 28911.4 Conclusions 290Acknowledgements 292References 29212 Applications of Phosphorus-Based Materials in Optoelectronics 295Matthew P. Duffy, Pierre-Antoine Bouit, and Muriel Hissler12.1 Introduction 29512.2 Phosphines 29612.2.1 Application as Charge-Transport Layer 29612.2.2 Application as Host for Phosphorescent Complexes 29912.2.3 Application as Emitting Materials 30312.3 Four-Membered P-Heterocyclic Rings 30612.3.1 Diphosphacyclobutanediyls 30612.3.2 Phosphetes 30712.4 Five-Membered P-Heterocyclic Rings: Phospholes 30712.4.1 Application as Charge-Transport Layers 30812.4.2 Application as Host for Phosphorescent Complexes 30912.4.3 Application as Emitter in OLEDs 30912.4.4 Dyes for Dye-Sensitized Solar Cells (DSSCs) 31612.4.5 Donors in Organic Solar Cells (OSCs) 31612.4.6 Application in Electrochromic Cells 31712.4.7 Application in Memory Devices 31812.5 Six-Membered P-Heterocyclic Rings 31912.5.1 Phosphazenes 31912.5.1.1 Application as Electrolyte for Solar Cells 31912.5.1.2 Application as Host for Triplet Emitters in PhOLEDs 32012.5.1.3 Application as Emitter for OLEDs 32112.6 Conclusion 321Abbreviations 322References 32413 Main-Chain, Phosphorus-Based Polymers 329Klaus Dück and Derek P. Gates13.1 Introduction 32913.2 Polyphosphazenes 33013.3 Poly(phosphole)s 33313.4 Poly(methylenephosphine)s 33613.5 Poly(arylene-/vinylene-/ethynylene-phosphine)s 34113.6 Phospha-PPVs 34313.7 Poly(phosphinoborane)s 34513.8 Metal-Containing Phosphorus Polymers 34713.9 Additional P-Containing Polymers 34913.10 Summary 350Acknowledgements 351References 35114 Synthons for the Development of New Organophosphorus Functional Materials 357Robert J. Gilliard, Jr., Jerod M. Kieser, and John D. Protasiewicz14.1 General Introduction 35714.1.1 Phosphorus-Based Functional Materials 35714.1.2 Phosphorus Allotropes 35914.2 Phosphorus Transfer Reagents as Emerging Synthetic Approaches to Materials 36014.2.1 Introduction to Phosphorus Transfer Reagents 36014.2.2 Phosphaethynolate Salts 36014.2.3 Phospha-Wittig Reagents 36714.2.4 Phospha-Wittig–Horner Reagents 37114.2.5 Phosphadibenzonorbornadiene Derivatives 37314.3 Carbene-Stabilized Molecules as Phosphorus Reagents 37514.3.1 Introduction to Carbene Phosphorus Complexes 37514.3.2 N-Heterocyclic Carbene-Stabilized Phosphorus Complexes 37514.3.3 Cyclic (Alkyl)(Amino) Carbene-Stabilized Phosphorus Compounds 37614.3.4 Reactions of N-Heterocyclic Carbenes with Phosphaalkenes 37714.4 Conclusions and Outlook 378References 37915 Arsenic-Containing Oligomers and Polymers 383Hiroaki Imoto and Kensuke Naka15.1 Introduction 38315.2 Chemistry of Organoarsenic Compounds 38415.3 Arsenic Homocycles 38415.4 Development of C–As Bond Formation for Organoarsenic15.4.1 Classical Methodologies 38615.4.2 In Situ-Generated Organoarsenic Electrophiles from Arsenic Homocycles 38715.4.3 In Situ-Generated Organoarsenic Nucleophiles from Arsenic Homocycles 38815.4.4 Bismetallation Based on Arsenic Homocycles 38815.5 Properties of Poly(vinylene-arsine)s 39115.6 Properties of 1,4-Dihydro-1,4-diarsinines 39115.7 Properties of Arsole Derivatives 39415.8 Arsole-Containing Polymers 39615.9 Conclusions 399References 40016 Antimony-and Bismuth-Based Materials and Applications 405Anna M. Christianson and François P. Gabbaï16.1 Introduction 40516.2 Anion Binding and Sensing Applications 40616.3 Small-Molecule Binding 41816.4 Antimony and Bismuth Chromophores 42616.5 Conclusion 430References 43017 High Sulfur Content Organic/Inorganic Hybrid Polymeric Materials 433Jeffrey Pyun, Richard S. Glass, Michael M. Mackay, Robert Norwood, and Kookheon Char17.1 Introduction 43317.2 The Chemistry of Liquid Sulfur 43417.2.1 Ring-Opening Polymerization of Elemental Sulfur 43417.2.2 Synthesis of Inorganic Nanoparticles in Liquid Sulfur 43517.2.3 Inverse Vulcanization of Elemental Sulfur 43717.2.4 Transformation Polymerizations with Elemental Sulfur: Combining Inverse Vulcanization with Electropolymerization 44117.3 Waterborne Reactions of Polysulfides 44217.4 Controlled Polymerization with High Sulfur-Content Monomers 44217.5 Modern Applications of High Sulfur-Content Copolymers 44417.5.1 High Sulfur-Content Polymers as Cathode Materials for Li-S Batteries 44417.5.2 High Sulfur-Content Polymers as Transmissive Materials for IR Thermal Imaging 44517.6 Conclusion and Outlook 448Acknowledgements 448References 44918 Selenium and Tellurium Containing Conjugated Polymers 451Zhen Zhang, Wenhan He, and Yang Qin18.1 Introduction 45118.2 Selenium-Containing Conjugated Polymers 45218.2.1 Background 45218.2.2 Electron-Rich Homopolymers 45318.2.3 Donor–Acceptor (D-A) Copolymers 45718.2.3.1 Selenium-Containing Benzodithiophene-Benzothiadiazole (BDT-BT) Copolymer Derivatives 46018.2.3.2 Selenium-Containing Benzodithiophene-Thienothiophene (BDT-TT) Copolymer Derivatives 46218.2.3.3 Selenium-Containing Benzodithiophene-Diketopyrrolopyrrole (BDT-DPP) and Benzodithiophene-Thienopyrrole-4,6-dione (BDT-TPD) Copolymers 46518.3 Tellurium-Containing Conjugated Polymers 46718.3.1 Background 46718.3.2 Synthesis of Tellurium-Containing Polymers 46718.3.2.1 Early Examples of Insoluble Polymers 46718.3.2.2 Tellurium-Bridge Polymers 46918.3.2.3 Soluble Tellurophene-Containing Conjugated Polymers 46918.3.2.4 Regio-Regular Poly(3-alkyltellurophene) 47218.3.2.5 Other Tellurium-Containing Conjugated Polymers 47318.3.3 Application of Tellurium-Containing Conjugated Polymers 47318.4 Conclusions and Outlook 476References 47619 Hypervalent Iodine Compounds in Polymer Science and Technology 483Avichal Vaish and Nicolay V. Tsarevsky19.1 Introduction 48319.1.1 Historical 48319.1.2 Bonding in Hypervalent Iodine Compounds 48419.1.3 Patterns of Reactivity Relevant to Applications in Polymer Science and Technology 48619.2 Applications of Hypervalent Iodine Compounds in Polymer Science and Technology 48719.2.1 HV Iodine Compounds as Initiators for Polymerization 48719.2.1.1 Direct Application of HV Iodine Compounds 48719.2.1.2 Functional Radical Initiators Generated as a result of Ligand-Exchange followed by Homolysis 49319.2.2 Post-Polymerization Modifications using HV Iodine Compounds 49519.2.3 HV Iodine Groups as Structural Elements in Polymers 49619.2.3.1 Polymers with HV Iodine-Based Pendant Groups 49619.2.3.2 HV Iodine Groups as part of the Polymer Backbone 50519.3 Conclusions 508Acknowledgements 508References 508Index