Table of Contents

Title Page

List of Contributors

Chapter 1: Stille Polycondensation: A Versatile Synthetic Approach to Functional Polymers

1.1 Introduction
1.2 Reaction Mechanism
1.3 Reaction Conditions
1.4 Examples of Functional Materials Synthesized by Stille Polycondensation
1.5 Challenge and Outlook
1.6 Summary
References

Chapter 2: Suzuki Polycondensation

2.1 Introduction
2.2 Mechanism of Suzuki Coupling and Suzuki Polycondensation
2.3 Catalysts
2.4 Reaction Conditions for Suzuki Coupling
2.5 Side Reactions
2.6 AB versus AA/BB Suzuki Polycondensation
2.7 Monomer Purity, Stoichiometry, and Solvents
2.8 Monomers for SPC
2.9 Chain Growth SPC
2.10 Scope and Applications of SPC
2.11 Conclusion
References

Chapter 3: Controlled Synthesis of Conjugated Polymers and Block Copolymers

3.1 Introduction
3.2 Approaches to Controlled Polymerizations
3.3 End-Functionalized Polymers
3.4 Block Copolymers
3.5 Other Copolymers
References

Chapter 4: Direct (Hetero)arylation Polymerization

4.1 Introduction
4.2 First Examples of Direct (Hetero)arylation Polymerization
4.3 Selectivity and Reactivity Problems
4.4 En Route to Defect-Free Conjugated Polymers
4.5 Outlook
References

Chapter 5: Continuous Flow Synthesis of Conjugated Polymers and Carbon Materials

5.1 Introduction to Flow Chemistry
5.2 Conjugated Polymers
5.3 Carbon Materials
5.4 Material Processing
5.5 Summary
References

Chapter 6: Synthesis of Structurally Defined Nanographene Materials through Oxidative Cyclodehydrogenation

6.1 Introduction
6.2 Synthesis of Nanographene Molecules through Oxidative Cyclodehydrogenation
6.3 Bottom-Up Synthesis of Graphene Nanoribbons
6.4 Conclusions
References

Chapter 7: Photochemical and Direct C–H Arylation Routes toward Carbon Nanomaterials

7.1 Introduction
7.2 Photochemical Routes toward PAHs and Carbon Nanomaterials
7.3 Intramolecular Direct Arylation C–H
References

Chapter 8: Carbon-Rich Materials from sp-Carbon Precursors

8.1 Introduction
8.2 Carbyne
8.3 Solid-State Reactions of Polyynes: Topochemical Polymerizations
8.4 Diyne Polymerization
8.5 Tubular Structures
8.6 Beyond Diynes – Topochemical Polymerization of Polyynes
8.7 Toward “Nanographene”
8.8 Pentalenes
8.9 Modification of sp-Precursors with Tetracyanoethylene (TCNE)
8.10 Thermal Dimerization of Cumulenes
8.11 Outlook: From Solution to Surface?
8.12 Summarizing Comments
Acknowledgments
References

Index

End User License Agreement

List of Illustrations

Chapter 1: Stille Polycondensation: A Versatile Synthetic Approach to Functional Polymers

Figure Scheme 1.1 The Stille coupling reaction scheme.
Figure Scheme 1.2 Synthesis of aryltin compounds by Eaborn et al. [9].
Figure Scheme 1.3 Coupling of halides and organostannanes by Kosugi et al. [10–12].
Figure Schemes 1.4 Synthesis of PPT by Stille polycondensation [16, 17].
Figure 1.5 Synthesis of PPTs with metalloporphyrin or pendent carbazole units [18].
Figure Scheme 1.6 A simplified mechanism for Stille coupling [7, 19].
Figure Scheme 1.7 Formation of cis complex and cis–trans isomerization [19]. L = ligand.
Figure Scheme 1.8 Cyclic and open transition states [26, 27].
Figure Scheme 1.9 A ligand dissociation to form a T-shaped complex [29].
Figure Scheme 1.10 A more complex mechanism by Espinet et al. [20].
Figure Scheme 1.11 The structure of some bulky phosphine ligands [34–37].
Figure Scheme 1.12 Selectivity of ArCl over ArOTf in Stille coupling [37].
Figure Scheme 1.13 Bulky ligands assist Stille coupling [20].
Figure Scheme 1.14 Microwave conditions to shorten reaction time [54].
Figure Scheme 1.15 The structure of some polyimide polymers for second-order NLO [59–61].
Figure Scheme 1.16 Synthesis of polymers with NLO chromophores on side chains [62].
Figure Scheme 1.17 Synthesis of fluoro- and alkoxy-substituted PPVs for third-order NLO [63].
Figure Scheme 1.18 Synthesis of polythiophene derivatives for third-order NLO [64].
Figure Scheme 1.19 Synthesis of PPTs with tricyanodihydrofuran subunit for PR material [65]
Figure 1.20 Synthesis of a polyalkylthiophene polymer [71].
Figure Scheme 1.21 Synthesis of PTB polymers.
Figure Scheme 1.22 The structures of PBDTTPD [73, 84–86], PBnDT-DTBT [87], PBnDT-FTAZ [88], and PBDTT-DPP [89].
Figure Scheme 1.23 Synthesis of PDTP-DFBT [90], PffBT4T, PBTff4T, and PNT4T [42].
Figure Scheme 1.24 Synthesis of CPDT-BT polymer [91, 92].
Figure Scheme 1.25 Synthesis of Si-bridged CPDT-BT polymer [56].
Figure Scheme 1.26 Synthesis of Si- and Ge-bridged CPDT-TPD polymers [93–95].
Figure Scheme 1.27 Synthesis of IID-based polymers [96, 97].
Figure Scheme 1.28 Synthesis of lactam-based donor polymers [98–102].
Figure Scheme 1.29 Conjugated polymers based on thiophene, benzothiadiazole, and benzobis(thiadiazole) [103].
Figure Scheme 1.30 Synthesis of DTBT-IDT and DTABT-IDT [104].
Figure Scheme 1.31 The synthesis of PDI containing polymer and small molecule [105, 106].
Figure Scheme 1.32 Synthesis of NDI-based polymer P(NDI2OD-T2) [107–109].
Figure Scheme 1.33 Synthesis of PNDIT and PNDIS polymers [110–112].
Figure Scheme 1.34 Synthesis of BFI-based acceptor materials [113–116].
Figure Scheme 1.35 Some polythiophene derivatives for OFETs [119, 120].
Figure Scheme 1.36 Some IID-based polymers for OFETs [121–123].
Figure Scheme 1.37 DPP-based polymers for OFETs [117, 125–127].
Figure Scheme 1.38 Synthesis of soluble PPV derivatives [131, 132].
Figure Scheme 1.39 Synthesis of PPV-based random copolymers for P-OLED [132, 133].
Figure Scheme 1.40 Synthesis of PPyV polymers and their pyridinium forms [134].
Figure Scheme 1.41 Synthesis of random and regioregular PPyV polymers [136].
Figure Scheme 1.42 Synthesis of regioregular polythiophenes using Stille method [137].
Figure Scheme 1.43 Synthesis of V-shaped polythiophene V-PT [138].
Figure Scheme 1.44 Synthesis of some OFET polymers based on CPDT with different bridging atoms [139, 140].
Figure Scheme 1.45 Examples of polythiophenes that can detect purine and pyrimidine via H-bonds [141–143].
Figure Scheme 1.46 Synthesis of polythiophene sensor polymer and its interaction with metal ions [144].
Figure Scheme 1.47 Synthesis of phenylene–thiophene-based liquid crystal polymer.
Figure Scheme 1.48 Stille coupling in the total synthesis of rapamycin and dynemicin A [147, 148].
Figure Scheme 1.49 Reaction scheme of Suzuki coupling for conjugated polymers.
Figure Scheme 1.50 Reaction scheme for Kumada coupling.
Figure Scheme 1.51 Catalytic use of tin in Stille coupling [150, 151].
Figure Scheme 1.52 Ionic liquid supported Stille coupling [152].

Chapter 2: Suzuki Polycondensation

Figure Scheme 2.1 Suzuki reaction catalytic cycle.
Figure Scheme 2.2 Transmetallation process involving a quaternary boronate anion.
Figure Scheme 2.3 Relationship between pH and an organoboron compound's nature.
Figure Scheme 2.4 Transmetallation involving Pd-OR intermediates.
Figure Scheme 2.5 Reactions in the absence of base or catalyzed by weak bases.
Figure Scheme 2.6 Ligands for palladium-catalyzed Suzuki reactions.
Figure Scheme 2.7 Reactions facilitated by ligandless catalysts.
Figure Scheme 2.8 Water-soluble ligands.
Figure Scheme 2.9 The first reported microwave-assisted Suzuki polycondensation.
Figure Scheme 2.10 Side reactions of Suzuki coupling: (a) formation of homocoupling products; (b) B–C bond cleavage; and (c) ipso-coupling.
Figure Scheme 2.11 Phosphine-mediated aryl–aryl exchange.
Figure Scheme 2.12 Possible routes to phosphorus incorporation during Suzuki polycondensation.
Figure Scheme 2.13 AA/BB versus AB Suzuki polycondensation.
Figure Scheme 2.14 Some commercially available monomers for AA/BB SPC.
Figure Scheme 2.15 Synthesis of AB- and BB-type monomers via aryllithiums.
Figure Scheme 2.16 Halide–boronate exchange for producing monomers and polymers.
Figure Scheme 2.17 Direct borylation via transition metal-catalyzed C–H activation of arenes.
Figure Scheme 2.18 Boron-based monomers for producing PAVs or PAEs.
Figure Scheme 2.19 Synthesis of a cyclododecaphenylene by iterative Suzuki coupling.
Figure Scheme 2.20 Use of masking groups to protect boronic acids during Suzuki coupling.
Figure Scheme 2.21 A cascade Heck–Suzuki route to a PAV.
Figure Scheme 2.22 Modified Suzuki coupling using a triolborate.
Figure Scheme 2.23 The first example of SPC using dichloroarene monomers.
Figure Scheme 2.24 SPC by a chain growth mechanism.
Figure Scheme 2.25 Synthesis of ladder-type polyphenylenes using SPC.
Figure Scheme 2.26 Regioregular polythiophene- and thiophene-containing copolymers made by SPC.
Figure Scheme 2.27 Units which have been integrated into polymers by SPC.
Figure Scheme 2.28 Carbazole copolymers made by SPC for OPV applications.

Chapter 3: Controlled Synthesis of Conjugated Polymers and Block Copolymers

Figure Scheme 3.1 Mechanism of the catalyst transfer polycondensation, illustrated via the polymerization of thiophenes.
Figure Scheme 3.2 Poly(thiophene)s obtained in the case of unidirectional growth (a) or bidirectional growth (b).
Figure Scheme 3.3 Grignard metathesis and the effect of the catalyst on the regioregularity of the polymer (without LiCl).
Figure Scheme 3.4 The selective formation of only the desired isomer of the monomer can be achieved in two ways. This results in regioregular poly(thiophene)s.
Figure Scheme 3.5 Mechanism of the Pd(RuPhos) protocol.
Figure Scheme 3.6 Chain growth polymerization of 2-halothiophenes, exemplified for chlorodibutylpropylenedioxythiophene and SnCl₄ as the initiator.
Figure Scheme 3.7 Overview of the different methods for the synthesis of functionalized Ni initiators for KCTP.
Figure Scheme 3.8 Visualization of different isolated Ni complexes equipped with (protected) functionalized initiators.
Figure Scheme 3.9 Visualization of multifunctional external initiators.
Figure Scheme 3.10 Suzuki–Miyaura polymerization of fluorene with Pd(P^tBu₃)₂ as external initiator.
Figure Scheme 3.11 Overview of end groups resulting in mono-capped or di-capped polymer chains.
Figure Scheme 3.12 Different methods to obtain block copolymers.
Figure Scheme 3.13 All-conjugated block copolymers consisting of different conjugated moieties.

Chapter 4: Direct (Hetero)arylation Polymerization

Figure Schemes 4.1 Synthesis of thiophene-based molecules.
Figure 4.2 Thiophene-based organic materials prepared by direct (hetero)arylation [14].
Figure Scheme 4.3 First example of direct (hetero)arylation polymerization.
Figure Scheme 4.4 Synthesis of poly(3,4-alkylenedioxythiophene)s.
Figure Scheme 4.5 First efficient synthesis of regioregular poly(3-hexylthiophene) (P3HT) by DHAP.
Figure Scheme 4.6 Synthesis of a push–pull arene-based copolymer.
Figure Scheme 4.7 Synthesis of a push–pull hetero(arene) copolymer.
Figure Scheme 4.8 First conjugated polymers synthesized by DHAP.
Figure Scheme 4.9 Selectivity and reactivity issues.
Figure Scheme 4.10 Synthesis of a push–pull copolymer by DHAP.
Figure Scheme 4.11 Monomers bearing β-blocking groups.
Figure Scheme 4.12 Selectivity from a directing group.
Figure Scheme 4.13 Branched and cross-linked poly(3-hexylthiophene).
Figure Scheme 4.14 Structural defects in conjugated alternating copolymers: (a) branching and (b) homocoupling.
Figure Scheme 4.15 (a) Regiosymmetric AB-type monomers give polymers insensitive to homocoupling defects. (b) P3HT is an example of non-regiosymmetric polymer.
Figure Scheme 4.16 Screening of DHAP conditions for P3HT synthesis.
Figure Scheme 4.17 Synthesis of P3HS and P3HT: effect on the regioregularity (rr).
Figure Scheme 4.18 Synthesis of P(Cbz-alt-TBT) via DHAP: homocoupling defects.
Figure Scheme 4.19 Defect-free copolymers from time-controlled DHAP.
Figure Scheme 4.20 Arenes and heteroarenes coupling investigated in DHAP.
Figure Scheme 4.21 Coupling of unprotected thiophene units.
Figure Scheme 4.22 Possible sources of defects in DHAP.
Figure Scheme 4.23 Polymers synthesized by DHAP and studied in: (a) plastic solar cells and (b) organic field effect transistors and light-emitting diodes.
Figure Scheme 4.24 Polymers synthesized by DHAP and studied in: (a) electrochromic windows; (b) chemical sensors; (c) memory devices; and (d) gas storage.

Chapter 5: Continuous Flow Synthesis of Conjugated Polymers and Carbon Materials

Figure 5.1 Pictures illustrating conventional batch processing and flow chemistry. The top graphic is reproduced with permission from Tekno Scienze Publisher [5].
Figure 5.2 Monomer components used in Suzuki polycondensation to produce P1 and P2 for application in OLED devices.
Figure 5.3 Polymer synthesis via Suzuki polycondensation for (a) PFO; (b) PCDHTBT; and (c) the associated continuous flow setup.
Figure 5.4 Flow synthesis of (a) PTB by Stille coupling and (b) MEH-PPV by the Gilch method.
Figure 5.5 Synthesis of PBDT-BT by Stille or Suzuki polycondensation.
Figure 5.6 Flow synthesis of PiLEDOT by direct arylation in a column reactor.
Figure 5.7 Synthesis of (a) PBDTTPD and (b) PBDTTTz-4 by Stille polycondensation in flow.
Figure 5.8 (a) The distribution of the photovoltaic parameters (PCE, V_oc, FF, I_sc, and P_max) of 375 modules, processed with two different solvent combinations, represented as histograms. (b) I–V curves of a champion module from each of the two solvent combinations. (c) Roll-to-roll slot-die coating of the active layer. (d) Photograph of a finished module.
Figure 5.9 (a) Preparation of thiophene Grignard monomer and synthesis of P3HT via GRIM. (b) Schematic representation for the flow setup using Ni(dppp)Cl₂ and (c) nickel complex 24.
Figure 5.10 (a) Schematic of droplet reactor, comprising a droplet generator and coiled PTFE tubing in a temperature-stabilized oil bath; (b) close-up of the droplet generator; note, the droplet phase has been dyed with colored ink for clarity; and (c) photograph showing droplet flow through coiled PTFE tubing as the polymerization proceeds. The stated flow conditions correspond to a 2-min residence time in the oil bath.
Figure 5.11 The three-step reaction sequence to PCBtB in microfluidic reactors.
Figure 5.12 (a) General scheme showing the flow synthesis of PC₆₁BM and PC₇₁BM and (b) large-scale flow synthesis of PC₆₁BM.
Figure 5.13 Synthesis of indene-C₆₀ bisadduct (IC₆₀BA) and indene-C₇₀ bisadduct (IC₇₀BA) under (a) conventional batch reaction and (b) continuous flow conditions.
Figure 5.14 Illustration of the oxidation reaction of graphite flakes in the Couette–Taylor flow reactor. (a) Schematic diagram of Couette–Taylor flow reactor system. (b) Conceptual diagram of Vortex structure in the Couette–Taylor reactor.
Figure 5.15 Flow processing of P3HT solution to align polymer chains and produce ordered polymer aggregates.
Figure 5.16 (a) The UV–Vis spectrum of P3HT film with CU and MCU indicating various solution treatment conditions; films deposited from pristine (b,d) and flow processed (c,e) P3HT solution examined using the atomic force microscopy (b,c) and grazing incidence angle X-ray scattering (d, e).

Chapter 6: Synthesis of Structurally Defined Nanographene Materials through Oxidative Cyclodehydrogenation

Figure Scheme 6.1 Synthesis of meso-naphthodianthrone (2) through the oxidative cyclodehydrogenation of helianthrone (1) with AlCl₃ reported by Scholl and Mansfeld.
Figure Scheme 6.2 Synthesis of HBC 4 through the intramolecular oxidative cyclodehydrogenation of hexaphenylbenzene 3 under various conditions.
Figure Scheme 6.3 Examples of nanographene molecules synthesized through intramolecular oxidative cyclodehydrogenation.
Figure Scheme 6.4 Two-step synthesis of C₃ symmetrical nanographene molecule 15.
Figure Scheme 6.5 Synthesis of nanographene molecule 17 (C78) through the intramolecular oxidative cyclodehydrogenation of oligophenylene precursor 16 under different conditions.
Figure Scheme 6.6 Oxidative cyclodehydrogenation of hexaphenylbenzene derivatives with DDQ.
Figure Scheme 6.7 Synthesis of teranthenes 19 and quarteranthene 22 through the oxidative cyclodehydrogenation with DDQ/Sc(OTf)₃.
Figure Scheme 6.8 Oxidative cyclodehydrogenation of indolyl-pentapyrrolylbenzene 24 with BAHA.
Figure Scheme 6.9 Base-induced cyclodehydrogenation for the synthesis of rylene diimides.
Figure Scheme 6.10 Anionic cyclodehydrogenation of precursors 37 and 39 toward 1-azaperylene (38) and imidazo(naphtho)quinolizine 40, respectively.
Figure Scheme 6.11 Synthesis of “defective” nanographene molecules 42 and 45 with seven-membered rings.
Figure Scheme 6.12 Synthesis of warped nanographene molecules 49 with one five-membered ring and five seven-membered rings.
Figure 6.15 Synthesis of pyrrole-fused azacoronenes 61, 64, and 67.
Figure Scheme 6.13 Synthesis of tetrabenzo[8]circulenes 51 and PAH 53 with an eight-membered ring through the oxidative cyclodehydrogenation.
Figure Scheme 6.14 Synthesis of N-substituted HBCs 56 and 59 with pyrimidine rings.
Figure Scheme 6.16 Synthesis of S-containing nanographene molecules 69 and 71.
Figure Scheme 6.17 Synthesis of B-containing nanographene molecule 74 and B- and S-containing PAH 76.
Figure 6.5 (a) Synthesis of N-doped chevron-type GNR 119, GNR heterojunction 121, and B-doped N = 7 armchair GNR 124 through the surface-assisted polymerization and cyclodehydrogenation. (b,c) High-resolution STM images on Au(111) surfaces of (b) GNR 119 and (c) GNR heterojunction 121 with (b) partly overlaid DFT-based STM simulation model and a formula chemical structure. (d) Differential conductance dI/dV map observed at the bias voltage of −0.35 V. The heterostructure profiles seen in (c) are drawn as white dashed lines as a guide to the eye. Scale bars in (c) and (d) indicate 2 nm. (e,f) Atomic resolution AFM images of (e) GNR 124 and (f) B-doped N = 14 armchair GNR formed via the fusion of GNR 124 [114]a.
Figure 6.1 Surface-assisted cyclodehydrogenation of (a) CHP 77 to TBC 78 and (c) 6,6′-bipentacene precursor 79 to peripentacene 80. (b) High-resolution STM image of TBC 78. (
Figure Scheme 6.18 Structures of N = 9 armchair and N = 5 zigzag GNRs with instruction for counting the number “N.”
Figure Scheme 6.19 Synthesis of GNRs 84, 87, and 90 through A₂B₂-type Suzuki, AA-type Yamamoto, and AB-type Diels–Alder polymerization, respectively, followed by oxidative cyclodehydrogenation.
Figure Scheme 6.20 Synthesis of laterally extended GNRs 94, 97, and 100 through A₂B₂-type Suzuki, AA-type Yamamoto, and AB-type Diels–Alder polymerization, respectively, followed by oxidative cyclodehydrogenation.
Figure 6.2 Schematic illustration for the surface-assisted synthesis of N = 7 armchair GNR 103, starting from 10,10′-dibromo-9,9′-bianthryl (101).
Figure 6.3 (a) Synthesis of N = 7 and 13 armchair GNRs 103 and 106, respectively, as well as their heterojunction such as 107 through the surface-assisted polymerization and cyclodehydrogenation. (b–d) High-resolution STM images on Au(111) surfaces of (b) GNR 103, (c) GNR 106, and (d) GNR heterojunction 107 with (b,c) partly overlaid molecular models (light blue) and (b) partially overlaid DFT-based STM simulation (gray scale). Inset of (d) displays an STM image of a larger area with a variety of N = 7–13 GNR heterojunctions.
Figure 6.4 (a) Synthesis of N = 5 armchair GNR 110, cove-edge GNR 113, and N = 6 armchair GNR 116 through the surface-assisted polymerization and cyclodehydrogenation. (b–e) High-resolution STM images on Au(111) surfaces of (b) GNR 110, (c) GNR 113 [154], (d) PPP 115, and (e) N = 6 armchair GNR 116 with partly overlaid (b,c) chemical structures and (d,e) molecular models. (b) Inset: DFT-simulated STM image of GNR 110. GNR 116 displayed in (e) was prepared with annealing at ∼300 °C to avoid the chemisorption of Br radicals on the Au(111) surface.

Chapter 7: Photochemical and Direct C–H Arylation Routes toward Carbon Nanomaterials

Figure Scheme 7.1 Formation of phenanthrene from cis-stilbene using the photochemical dehydrogenation method.
Figure Scheme 7.2 Synthesis of contorted hexabenzocoronene using the Katz-modified Mallory reaction as the final synthetic step.
Figure Scheme 7.3 Synthesis of hexabenzocoronene from substituted pentacene quinone core.
Figure Scheme 7.4 Synthesis of thiophene-fused hexabenzocoronenes with different peripheral substituents.
Figure Scheme 7.5 Regioselective synthesis of fused perylenediimide molecules.
Figure Scheme 7.6 Synthesis of fused perylenediimide molecules.
Figure Scheme 7.7 Synthesis of fused perylenediimide molecules.
Figure Scheme 7.8 Synthesis of PDI-based fused dimers.
Figure Scheme 7.9 Synthesis of pyridine-fused PDIs.
Figure Scheme 7.10 Synthesis of PAHs prepared using the CDH reaction.
Figure Scheme 7.11 Photochemical synthesis of dibenzo[fg,op]naphtacene derivatives with liquid crystalline properties.
Figure Scheme 7.12 Synthesis of PAHs through the photochemical cyclodehydrohalogenation (CDH) reaction. The yields per cyclization reaction are given in parentheses.
Figure Scheme 7.13 Photochemical synthesis of heterocycle-fused molecules.
Figure 7.1 Intramolecular palladium-catalyzed arylation and key intermediates for the proposed mechanism by Rice et al.
Figure Scheme 7.14 Synthesis of dibenzo[a,g]corannulene by palladium-catalyzed intramolecular direct C–H arylation.
Figure Scheme 7.15 Synthesis of picene derivatives by palladium-catalyzed intramolecular direct C–H arylation.
Figure Scheme 7.16 Synthesis of indeno[1,2,3]-annelated PAHs by palladium-catalyzed intramolecular direct C–H arylation.
Figure Scheme 7.17 Synthesis of indenopyrenes by palladium-catalyzed intramolecular direct C–H arylation.
Figure Scheme 7.18 Synthesis of pentaindenocorannulene and tetraindenocorannulene from multiple palladium-catalyzed intramolecular direct C–H arylation.
Figure Scheme 7.19 Synthesis of corannulene and sumanene from multiple intramolecular palladium-catalyzed direct C–H arylation.
Figure Scheme 7.20 Sequential ICl-induced alkyne cyclization followed by an intramolecular direct C–H arylation.
Figure Scheme 7.21 Synthesis of low π-sextet PAHs by palladium-catalyzed intramolecular direct C–H arylation.

Chapter 8: Carbon-Rich Materials from sp-Carbon Precursors

Figure 8.1 TEM images of carbon structures formed by pyrolysis of acetylenic scaffolds, (a) carbon onions, (b) carbon nanotubes containing cobalt, (c) carbon nanotubes containing iron, and (d) carbon “ropes.”
Figure 8.2 Schematic chemical structures of α-carbyne, β-carbyne, polyynes, and cumulenes.
Figure 8.3 Schematic formation of a polyyne with sterically demanding end groups from a trialkylsilyl-protected precursor.
Figure 8.4 Schematic structure of polyynes encased in a (a) single-walled and (b) double-walled carbon nanotube.
Figure 8.5 (a) Schematic formation of a polyyne rotaxane via active metal templation. Polyyne rotaxanes from the groups of (b) Saito, see [39], (c) Gladysz, see [40–42], (d) Anderson and Tykwinski, see [43, 44], and (e) Anderson, see [45].
Figure 8.6 Synthesis of a hexayne [3]rotaxane by Frauenrath and coworkers, using α-cyclodextrins.
Figure 8.7 Schematic depiction of the synthesis of “odd” [n]cumulenes and the formation of a [9]cumulene rotaxane.
Figure 8.8 Schematic crystal packing for several modes of polyyne polymerization, and optimal parameters θ, R, and d for each addition pattern. (a) Polydiacetylene formation via 1,4-addition of a diyne moiety, leading to a ladder polymer formation via a second 1,4-addition. (b) Polydiacetylene formation via 3,6-addition of a diyne moiety. (c) Polytriacetylene formation via 1,6-addition of a triyne moiety. (d) Polytetraacetylene formation via 1,8-addition of a tetrayne.
Figure 8.9 Goroff's supramolecular approach to PIDA/PBDA formation from diiodo- or dibromo-1,3-butadiynes.
Figure 8.10 Schematic description of Campos' polydiphenyldiacetylene (PDPDA) formation templated by a functionalized block copolymer.
Figure 8.11 Morin's PDA formation via (a) a meta-linked dimeric phenylene butadiynylene derivative and (b) a para-linked oligo(phenylene butadiynylene).
Figure 8.12 (a) Chemical structure of 1a–c (b–d) observed molecular stacking of macrocycles 1a–c, respectively.
Figure 8.13 (a) Chemical structure of 2, (b) molecular stacking of monomer 2, and (c) structure of the polymer obtained by slow annealing of 2 at 40 °C, (d) chemical structure of 3, (e) solid-state stacking of monomer 3, and (f) solid-state structure of the polymer obtained by slow annealing of 3 at 190 °C.
Figure 8.14 (a) Chemical structures of Morin's substituted phenylacetylenyl and phenylbutadiynyl macrocycles (PAM/PBM) for organic nanotube/nanorod formation. (b) Schematic depiction of topochemical polymerization of macrocycles.
Figure 8.15 (a) Fowler's supramolecular host–guest approach toward a polytriacetylene and (b) crystallographic investigation before and after irradiation.
Figure 8.16 X-ray analysis of Frauenrath's substituted octa-2,4,6-triyne-1,8-diol derivatives for either 1,4- or 1,6-polymerization.
Figure 8.17 Tetraynes with packing parameters suitable for 1,6-addition polymerization. (a) θ = 30°, R_1,6 = 3.7 Å, R_3,8 = 3.7 Å, and d = 7.4 Å; (b) θ = 28°, R_1,6 = 3.7 Å, R_3,8 = 3.6 Å, and d = 7.7 Å; and (c) θ = 29°, R_1,6 = 3.5 Å, R_3,8 = 3.5 Å, and d = 7.5 Å.
Figure 8.18 (a) Chemical structure of nonamphiphilic hexayne 7 and amphiphilic hexayne 8. (b) Structural depiction of the self-assembly of amphiphile 8 into colloids in aqueous solution and polymerization into carbonized nanocapsules under UV irradiation.
Figure 8.19 (a) Chemical structure of hexayne amphiphile 9, (b) predicted structural model for self-assembled monolayers of 9 at the air–water interface, and (c) close packing of hexayne outlining parameters significant for topochemical polymerization: tilt angle θ = 62.5° relative to the normal layer, short contact between the acetylene carbons of neighboring molecules 3.42–3.53 Å along the a-axis, and packing distance 5.20 Å.
Figure 8.20 Dichtel's Asao–Yamamoto benzannulation reaction toward 2,3-diarylnaphthalenes.
Figure 8.21 Alabugin's (a) Wolff–Kishner-type reaction toward tetracenediones and (b) examples of radical intramolecular cascade reactions.
Figure 8.22 Selected reactions toward pentalenes (a) Itami's C–H activation protocol mediated by Pd/Ag and (b,c) Diederich's protocol mediated by Pd/Zn.
Figure 8.23 (a) Chemical structure of the dendritic “molecular battery” 11 from 12-fold addition of TCNE. (b) Cascade procedure to form [AB]-type oligomer 13 with a dendralene backbone.
Figure 8.24 Cyano-functionalized diaryltetracenes through [2+2] cycloaddition of TCNE with tetraaryl[3]cumulenes, and ORTEP drawing of parent derivative (R=H).
Figure 8.25 Products from the reaction of a [5]cumulene with TCNE.
Figure 8.26 Thermal dimerization of [5]-, [7]-, and [9]cumulenes.
Figure 8.27 (a) Synthetic route toward cove-edged GNRs, where blue highlights Clar sextets consistent with the two most likely canonical structures, 25[1] and 25[1]′; ORTEP drawing of 25[1]. (b) Chemical structure of cove-edged GNR 26 grown on a Au(111) surface under UHV conditions. (c) Long-range STM image of the oligomers after cyclodehydrogenation. (d) High-resolution STM image of isolated GNR with structural model superimposed.
Figure 8.28 (a) Chemical structures of the glycosylated and ester-terminated hexaynes 27 and 28, respectively, while (b,c) show STM images of 28 on a Au(111) at low temperatures, with submolecular resolution. The islands show two different contrasts within the ribbons, which are 2.3-nm wide and appear in pairs with a width of 4.6 nm. Molecules are ordered in a head-to-head and tail-to-tail motif with head (blue) and tail (red).
Figure 8.29 (a) Schematic synthesis of oligo-(E)-1,1′-bi(indenylidene) through thermally induced C1–C5 radical cyclizations of enediyne precursors followed by step growth polymerization on Au(111). (b) Nc-AFM image of an individual oligomer chain. (c) Experimental STM dI/dV map (constant height) at V_s = 0.125 V reveals an extended electronic state along the conjugated backbone of oligomer shown in (b).
Figure 8.30 (a) Chemical structure of 1,3,5-tris-(4-ethynylphenyl)benzene (exTEB), (b) trimer after cyclotrimerization of exTEB on Au(111), (c) STM image of trimer on Au(111), (d) hexamer after cyclotrimerization of exTEB on Au(111), (e) STM image of hexamer on Au(111), and (f) honeycomb-like polyphenylene nanostructures after annealing at 433 K on Au(111).
Figure 8.31 (a) Chemical structure of 1,3,5-triethynylbenzene (TEB). STM topographic images of (b) TEB molecules and reaction products on Ag(111) showing both TEB molecules (green) and dimeric products (red), and (c) carbon network after annealing a dimer-dominated sample to 370 K. (d) Chemical structure of exTEB. STM topographic images of (e) exTEB molecules and reaction products on Ag(111) showing covalently bonded exTEB dimers after annealing at 300 K (lower inset shows a high-resolution image of a dimer superimposed with a calculated model and the upper inset magnifies an area with dimers in red and monomers in green), and (f) a magnified area of the network after annealing to 400 K. (Inset shows a single honeycomb segment superimposed with a calculated model.) Scale bars in (b) and (c) denote 10 Å while those in (e) and (f) denote 50 nm.
Figure 8.32 (a) Schematic depiction of the elaboration of corannulene into sp² carbon allotropes and the analogous carbomerization into sp²/sp carbon allotropes (graphynes) and (b) example of a carbomer synthesized by Chauvin and coworkers (with X-ray crystal structure).

List of Tables

Chapter 2: Suzuki Polycondensation

Table 2.1 Aryl–aryl interchange (10 to 12) measured at 50 °C after 3 h in CDCl₃

Chapter 5: Continuous Flow Synthesis of Conjugated Polymers and Carbon Materials

Table 5.1 Reaction conditions of flow and batch reactions and the molecular weight data of the resulting polymers P1 and P2
Table 5.2 Reaction conditions^a and molecular mass data^b for Suzuki polycondensations in batch and flow
Table 5.3 Reaction conditions and molecular mass data^a for PTB synthesized using Stille polycondensation^b (entries 1–4) and MEH-PPV synthesized using the Gilch method^c (entries 5 and 6) in batch and flow

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List of Contributors

Serge Beaupré
Université Laval
Department of Chemistry
Pavillon Alexandre-Vachon
Quebec City, QC G1V 0A6
Canada

Maxime Daigle
Université Laval
Département de chimie et Centre de recherche sur les matériaux avancés (CERMA)
1045 Ave de la Médecine
Québec G1V 0A6
Canada

Maude Desroches
Université Laval
Département de chimie et Centre de recherche sur les matériaux avancés (CERMA)
1045 Ave de la Médecine
Québec G1V 0A6
Canada

Andrew C. Grimsdale
Nanyang Technological University
School of Materials Science and Engineering
Block N4.1, 50 Nanyang Avenue
Singapore 639798
Singapore

Tine Hardeman
KU Leuven
Department of Chemistry
Celestijnenlaan 200F, bus 2404
3001 Heverlee
Belgium

Guy Koeckelberghs
KU Leuven
Department of Chemistry
Celestijnenlaan 200F, bus 2404
3001 Heverlee
Belgium

Anurag Krishna
Nanyang Technological University
School of Materials Science and Engineering
Block N4.1, 50 Nanyang Avenue
Singapore 639798
Singapore

Mario Leclerc
Université Laval
Department of Chemistry
Pavillon Alexandre-Vachon
Quebec City, QC G1V 0A6
Canada

Andrey V. Lunchev
Nanyang Technological University
School of Materials Science and Engineering
Block N4.1, 50 Nanyang Avenue
Singapore 639798
Singapore

Valerie D. Mitchell
University of Melbourne
School of Chemistry, Bio21 Institute
Bldg. 102, Room 438, 30 Flemington Road
Parkville, VIC 3010
Australia

Jean-Francois Morin
Université Laval
Département de chimie et Centre de recherche sur les matériaux avancés (CERMA)
1045 Ave de la Médecine
Québec G1V 0A6
Canada

Akimitsu Narita
Max-Planck-Institut für Polymerforschung
Ackermannweg 10
55128 Mainz
Germany

Dominik Prenzel
Friedrich-Alexander-University Erlangen-Nürnberg (FAU)
Department of Chemistry and Pharmacy Interdisciplinary Center for Molecular Materials (ICMM)
Henkestrasse 42
91054 Erlangen
Germany

Alexander M. Schneider
University of Chicago
Department of Chemistry
929 E. 57th St. GCIS E 419 A
Chicago, IL 60637
USA

Rik R. Tykwinski
Friedrich-Alexander-University Erlangen-Nürnberg (FAU)
Department of Chemistry and Pharmacy Interdisciplinary Center for Molecular Materials (ICMM)
Henkestrasse 42
91054 Erlangen
Germany

Marie-Paule Van Den Eede
KU Leuven
Department of Chemistry
Celestijnenlaan 200F, bus 2404
3001 Heverlee
Belgium

Lize Verheyen
KU Leuven
Department of Chemistry
Celestijnenlaan 200F, bus 2404
3001 Heverlee
Belgium

Wallace W.H. Wong
University of Melbourne
School of Chemistry, Bio21 Institute
Bldg. 102, Room 438, 30 Flemington Road
Parkville, VIC 3010
Australia

Luping Yu
University of Chicago
Department of Chemistry
929 E. 57th St. GCIS E 419 A
Chicago, IL 60637
USA

Tianyue Zheng
University of Chicago
Department of Chemistry
929 E. 57th St. GCIS E 419 A
Chicago, IL 60637
USA