Synthesis and ring-opening metathesis polymerisation of <i>o</i>-alkoxy benzothiadiazole paracyclophane-1,9-dienes

Janpatompong, Yurachat; Komanduri, Venukrishnan; Khan, Raja U; Turner, Michael L.

doi:10.1039/d2ob01989b

Cited by 3 publications

(2 citation statements)

References 41 publications

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“…Carbazole pendant polymers, which attach a carbazole unit to a nonconjugated polymer backbone like PVC, are popular due to their unique physical properties. They exhibit photoconductivity and resistance to high temperatures, making them versatile materials used in electrical insulators, hole-transport materials, OLED components, photovoltaic devices, and electro-optics [18][19][20][21][22][23][24][25] . They also serve as hole-transporting and electron-blocking layers in OLEDs.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Characterization, and Optical Properties of Carbazole-Functionalized Poly(norbornene-dicarboximide) by ROMP

Mahmoud Z. Basyouni,

Mohammed F. Radwan,

Mohamed E. Abdu

et al. 2024

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A novel norbornene-dicarboximide monomer functionalized with carbazole was synthesized and effectively polymerized using the Grubbs 3 rd generation initiator. Extensive characterization through NMR, GPC, FT-IR, DSC, and UV-vis spectroscopy confirmed the polymer's characteristics. The polymer demonstrated the anticipated nearly 1:1 vinylene cis-trans microstructure, possessing a molecular weight of 26800 g/mol and a polydispersity index of 1.11. Its glass transition temperature, as determined by DSC, was 117 °C. UV-vis analysis confirmed the presence of the polymer-bound carbazole group, evidenced by a λ max of 220 nm, compared to 222 nm for carbazole and 221 nm for the monomer.

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Section: Introductionmentioning

confidence: 99%

Synthesis, Characterization, and Optical Properties of Carbazole-Functionalized Poly(norbornene-dicarboximide) by ROMP

Mahmoud Z. Basyouni,

Mohammed F. Radwan,

Mohamed E. Abdu

et al. 2024

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“…The pCpd scaffold has been synthesized to incorporate alkyl and alkoxy , side-chains, benzothiadiazoles, − and a bromine atom for a palladium-catalyzed cross-coupling reaction. , These limited structural modifications to pCpd’s decks, especially when compared to its structural analogue [2.2]paracyclophane, , can be attributed to the harsh reaction conditions required to install the alkene “bridges” (Scheme ) and the sensitivity of the carbon–carbon double bonds to reaction conditions . As a result, this dearth of structural modifications to pCpd limits the applications of PPVs synthesized from these monomers.…”

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confidence: 99%

Functionalized [2.2]Paracyclophanedienes as Monomers for Poly(p-phenylenevinylene)s

Mann,

Wang,

Dumlao

et al. 2024

ACS Macro Lett.

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Poly(p-phenylenevinylene)s (PPVs) featuring complex side-chains, to date, have only been synthesized by nonliving polymerization methods which have no control over PPV molecular weights, dispersities, or end groups. [2.2]-Paracyclophane-1,9-diene (pCpd) has gained attention as a monomer for its ability to be ring-opened to PPV in a living fashion. pCpd, an organic cyclic scaffold with planar chirality, has seen minimal structural diversity due to the harsh reaction conditions required to afford the highly strained compound. Herein, we introduce a general method to overcome this by targeting the synthesis of a monohydroxy-pCpd via monodemethylation of a dialkoxy-pCpd. The monohydroxy-pCpd can then be functionalized easily, which we demonstrate using three distinct side-chains with four moieties commonly incorporated in conjugated polymers: an alkyl bromide, an oligo(ethylene glycol) chain, an enantiomerically pure side-chain, and a Boc-protected amine. These monofunctionalized-pCpds were investigated as monomers in the ring-opening metathesis polymerization (ROMP) to afford functionalized PPVs in a living manner. The functionalgroup-containing PPVs are synthesized with full control over their end groups, repeat units, and dispersities. The feasibility of postpolymerization modifications to incorporate any desired moiety to PPV fabricated by this method was demonstrated using an azide− alkyne click reaction. All synthesized PPVs were soluble in organic solvents and display the same fluorescent emission, indicating their conjugated backbones are unaltered.

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Molecular Insights into [2.2]Paracyclophane‐Based Functional Materials: Chemical Aspects Behind Functions

Hassan

2024

Adv Funct Materials

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Many of the functions and features of practically useful materials are the province of molecular‐level chemistry and their modulation at different length‐scale. This report illustrates the molecular‐level chemistry behind functions and features of the [2.2]paracyclophane‐based materials with a particular focus on the most recent explorations on through‐space conjugated small‐molecule organic emitters, π‐stacked macrocyclic molecules and polymers, poly(p‐phenylenevinylene)s featuring well‐defined donor‐acceptors sequence control, and surface engineering of technologically‐relevant parylenes that finds broad applications across the field of chemical science and technology. This report largely deals with the potential and opportunities associated with molecular features and functions of planar chirality, conformational behaviors, strain‐induced non‐planarity of the aromatics, the profound impacts of through‐space conjugation and π‐electron interactions/delocalization on optoelectronic properties of the π‐conjugated organic emitters, polymers and extended structures consisting of cyclophanes. A special focus is put on the concept of supramolecular polymers using chemically‐programmed chiral cyclophanes via non‐covalent stacking and controlled conformational arrangements. Illustrating cyclophane as precursors/monomers and fabrication strategies for their incorporation in structurally‐controlled (poly(p‐xylylene)s formed via chemical vapor deposition polymerization and post‐deposition fabrication for interface engineering is described. Demonstrating a rather different approach of electronically‐dictated ring‐opening metathesis polymerization employing strained cyclophane‐diene precursors that generate conjugated poly(p‐phenylenevinylene)s with well‐defined (i.e., low dispersity) and donor‐acceptor sequence control is also discussed. This report will serve as an indispensable one‐stop reference for organic, and polymer chemists, as well as material scientists working with cyclophanes for research innovations.

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Synthesis and ring-opening metathesis polymerisation of o-alkoxy benzothiadiazole paracyclophane-1,9-dienes

Abstract: Ortho-diethylhexyloxyphenylene benzothiadiazole paracyclophane-1,9-diene as a mixture of diastereomers was synthesized by a sequential benzyne Stevens rearrangement, oxidation and pyrolysis of a dithia[3.3]paracyclophane. Reaction of these highly strained cyclophanedienes with the...

Cited by 3 publications

References 41 publications

Synthesis, Characterization, and Optical Properties of Carbazole-Functionalized Poly(norbornene-dicarboximide) by ROMP

Synthesis, Characterization, and Optical Properties of Carbazole-Functionalized Poly(norbornene-dicarboximide) by ROMP

Functionalized [2.2]Paracyclophanedienes as Monomers for Poly(p-phenylenevinylene)s

Molecular Insights into [2.2]Paracyclophane‐Based Functional Materials: Chemical Aspects Behind Functions

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