Through‐Space Conjugated Polymers

Morisaki, Yasuhiro; Chujo, Yoshiki

doi:10.1002/9783527632664.ch5

Cited by 9 publications

(3 citation statements)

References 152 publications

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“…The success of this design relies on the precise chain-end modification of the redox-active polymers. Hence, the design and synthetic approach of the target architecture are based on the following criteria: (1) Triarylamines-containing monomers are selected to ensure quantitative functionalization in the latter polymer, while the attached vinyl group ensures minimal spatial separation of the redox-active polymer with maximal through-space interaction. , (2) A novel Ru II (dqp) 2 -based (dqp is 2,6-di(quinolin-8-yl)pyridine) complex serves as the photoactive unit, which typically displays excited-state lifetimes in the microsecond time scale at room temperature. − (3) The nitroxide-mediated polymerization using functional initiators allows the direct preparation of functional telechelic polymers, which can be further utilized to reinitiate NMP or to introduce the ruthenium complex. In the first part of this work, the polymerization kinetics are investigated by SEC, NMR spectroscopy, and complemented by mass spectrometry.…”

Section: Introductionmentioning

confidence: 99%

Nitroxide-Mediated Polymerization of Styrenic Triarylamines and Chain-End Functionalization with a Ruthenium Complex: Toward Tailored Photoredox-Active Architectures

et al. 2013

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The preparation of redox-active polymers and the chainend functionalization with one ruthenium complex was investigated in detail. A series of substituted monomers, i.e., styrenic triarylamines bearing methyl, fluoro, or methoxy substituents, were prepared by a one-pot Hartwig−Buchwald coupling. The nitroxide-mediated polymerization (NMP) was studied by variation of the functional initiators, the monomer-to-initiator ratios, and the solvent. The kinetic analysis of the prototypical methyl-substituted triarylamine shows the controlled polymerization up to 75% conversion, but a considerable decrease of the polymerization rate was observed during the course of the reaction. Both chain-end functionalities of the purified oligomers were subsequently utilized, i.e., the nitroxide to serve as a macroinitiator for an additional NMP step and the chloromethyl group to introduce one ruthenium complex at the chain terminus. The products were analyzed in detail by size-exclusion chromatography, NMR spectroscopy, and mass spectrometry. The optical and electrochemical properties of the prepared poly(triarylamine)s show the application potential as charge transport materials in conjunction with the photoactive ruthenium complex.

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Section: Introductionmentioning

confidence: 99%

Nitroxide-Mediated Polymerization of Styrenic Triarylamines and Chain-End Functionalization with a Ruthenium Complex: Toward Tailored Photoredox-Active Architectures

et al. 2013

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“…Besides this main field of application, polymers and oligomers containing cyclophane units are studied as very useful materials for electric and optical devices due to their remarkable electronic and structural properties. It should be first emphasized that π-conjugated polymers with cyclic oligomers in their structures show interesting luminescent, transport, or nonlinear optical properties; thus, they can be used in OLEDs, photovoltaic devices, wave guides, and molecular wires. − Physicochemical properties of cyclophanes differ significantly from those of linear compounds due to their particular structures causing their electronic interactions to occur through-space and/or through-bond. Through-space interaction was used by Isuoka et al for the preparation of organic magnetic materials.…”

Section: Introductionmentioning

confidence: 99%

High-Spin Polymers: Ferromagnetic Coupling of S = 1 Hexaazacyclophane Units up to a Pure S = 2 Polycyclophane

et al. 2017

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Triarylamines oxidized to radical cations can be used as stable spins sources for the design of high-spin compounds. Here, we present the synthesis of the polyarylamine-containing hexaazacyclophanes linked via meta-terphenyl bridges. Spins, created after oxidation of the polymer, can be coupled magnetically in cyclophane moieties via meta-phenyl and along the polymer chain via meta-terphenyl units. The formation of a quintet spin state was evidenced by pulsed-EPR nutation spectroscopy. Two exchange coupling constants via both couplers were determined experimentally and corresponded to J/k = 89 K in the cyclophane moiety and j/k = 17 K via meta-terphenyl. Most importantly, in this polymer, four spins can be ferromagnetically ordered via both couplers, which leads to the high spin state.

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“…The compound [2.2]paracyclophane (pCp) and its derivatives constitute a well-known class of aromatic compounds characterized by an unusual three-dimensional framework and unique through-space interactions between their stacked aromatic subunits . First discovered in the late 1940s, these molecules find nowadays wide applications in material sciences for the development of through-space conjugated polymers and optoelectronic devices …”

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confidence: 99%

Highly Enantioselective Desymmetrization of Centrosymmetric pseudo-para-Diformyl[2.2]paracyclophane via Asymmetric Transfer Hydrogenation

et al. 2018

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Herein we describe the desymmetrization of a centrosymmetric pseudo-para-diformyl[2.2]paracyclophane based on Noyori asymmetric transfer hydrogenations (ATH). The reduction proceeds smoothly in the presence of commercially available ruthenium complexes to afford a monohydroxymethylated product in good yields and excellent enantioselectivities (up to 74% isolated yield and 99% ee). Our approach is operationally simple and can be run in gram-scale without any significant loss in the reaction efficiency. This desymmetrization strategy allows an easy access to an enantiopure compound bearing on each aromatic ring of the pCp core different reactive groups suitable for regioselective orthogonal postfunctionalization.

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Through‐Space Conjugated Polymers

Cited by 9 publications

References 152 publications

Nitroxide-Mediated Polymerization of Styrenic Triarylamines and Chain-End Functionalization with a Ruthenium Complex: Toward Tailored Photoredox-Active Architectures

Nitroxide-Mediated Polymerization of Styrenic Triarylamines and Chain-End Functionalization with a Ruthenium Complex: Toward Tailored Photoredox-Active Architectures

High-Spin Polymers: Ferromagnetic Coupling of S = 1 Hexaazacyclophane Units up to a Pure S = 2 Polycyclophane

Highly Enantioselective Desymmetrization of Centrosymmetric pseudo-para-Diformyl[2.2]paracyclophane via Asymmetric Transfer Hydrogenation

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