Precise One-Pot Synthesis of End-Functionalized Conjugated Multi-Block Copolymers via Combined Olefin Metathesis and Wittig-type Coupling

Nomura, Kotohiro; Haque, Tahmina; Onuma, Taira; Hajjaj, Fatin; Asano, Motoko S.; Inagaki, Akiko

doi:10.1021/ma4022554

Cited by 30 publications

(38 citation statements)

References 86 publications

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“…The promising characteristics by adopting this approach can be summarized as follows: (1) the resultant polymers are defect-free (without termination of the conjugated units, without containing any negative impurities such as halogen, sulfur), (2) the resultant polymers (oligomers) possessed highly trans olefinic double bonds (because, as initially proposed by Thorn-Csányi et al [7,8,[11][12][13][14], the reaction proceeds via metallacycle intermediate, Scheme 3). Moreover, the resultant polymers prepared by Ru catalyst possessed well-defined polymer chain ends (as vinyl group) [22,[25][26][27][28][29][30]; therefore, modification of the conjugated materials can be demonstrated by utilization of the chain ends [25][26][27][28][29][30]. Scheme 3.…”

Section: Methodsmentioning

confidence: 99%

“…A precise, one-pot synthesis of end-functionalized block copolymers consisting of PFVs and oligo(2,5-dialkoxy-1,4-phenylene vinylene) or terthiophene units as the middle segment could be prepared by olefin metathesis of the vinyl group in the PFV chain ends followed by subsequent Wittig-type coupling [29]. As shown in Scheme 7, two approaches were considered for this purpose.…”

Section: Precise One-pot Synthesis Of End-functionalized Conjugated Mmentioning

confidence: 99%

“…Table 2. Synthesis of triblock copolymers with well-defined end functional groups [29]. We have shown that a facile, efficient synthesis of ABCBA type amphiphilic block copolymers has been established in a precise manner (as a rare example) by attachment of PEG into the both chain ends of the all-trans, defect-free, high molecular weight PFVs.…”

Section: Precise One-pot Synthesis Of End-functionalized Conjugated Mmentioning

confidence: 99%

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Acyclic Diene Metathesis (ADMET) Polymerization for Precise Synthesis of Defect-Free Conjugated Polymers with Well-Defined Chain Ends

Haque

Nomura

2015

Catalysts

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This accounts introduces unique characteristics by adopting the acyclic diene metathesis (ADMET) polymerization for synthesis of conjugated polymers, poly(arylene vinylene)s, known as promising molecular electronics. The method is more suitable than the other methods in terms of atom efficiency affording defect-free, stereo-regular (exclusive trans) polymers with well-defined chain ends; the resultant polymers possess better property than those prepared by the conventional methods. The chain ends (vinyl group) in the resultant polymer prepared by ruthenium-carbene catalyst(s) can be modified by treating with molybdenum-alkylidene complex (olefin metathesis) followed by addition of various aldehyde (Wittig type cleavage), affording the end-functionalized polymers exclusively. An introduction of initiating fragment, the other conjugated segment, and one-pot synthesis of end-functionalized block copolymers, star shape polymers can be achieved by adopting this methodology.

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Section: Methodsmentioning

confidence: 99%

Section: Precise One-pot Synthesis Of End-functionalized Conjugated Mmentioning

confidence: 99%

Section: Precise One-pot Synthesis Of End-functionalized Conjugated Mmentioning

confidence: 99%

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Acyclic Diene Metathesis (ADMET) Polymerization for Precise Synthesis of Defect-Free Conjugated Polymers with Well-Defined Chain Ends

Haque

Nomura

2015

Catalysts

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“…Moreover, their fluorescence life times (λ em = 530 -609 nm in THF) (τ = 0.654, 0.746, 0.697 ns, respectively) are longer than those in the others (0.521, 0.534 ns, respectively). The emission intensities were also influenced by the PFV conjugation length (FV repeat unit), and we assumed that the observed differences are thus due to an energy transfer from the PFV conjugated main chain to the oligo(thiophene)moieties (Figure 1) [45]. A facile one-pot synthesis of star shape (triarm) polymers containing a PFV main chain with well-defined end groups has also been achieved (Scheme 13) Scheme 13.…”

Section: Introduction Of End Functionality Into Conjugated Polymers Bmentioning

confidence: 99%

“…Although the above method enables precise and exclusive synthesis of the desired fully end-functionalized conjugated polymers [45] [46] using molybdenum-alkylidene catalyst, the direct chain transfer pathway [50] [51] [52] [53]…”

Section: Introduction Of End Functionality Into Conjugated Polymers Bmentioning

confidence: 99%

ADMET Polymerization: Greener Method for Synthesis of End-Functionalized Poly(Arylene Vinylene)s

Haque¹,

Nomura²

2017

GSC

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Recent results for synthesis of conjugated polymers, poly(arylene vinylene)s exemplified as poly(fluorene vinylene)s and poly(phenylene vinylene)s, by acyclic diene metathesis (ADMET) polymerization have been introduced. The methods using molybdenum and ruthenium catalysts afforded defect-free, high molecular weight polymers with all trans olefinic double bonds, and significant reduction of by-products (halogen, sulfur etc.) in addition of decrease of structurally defects have been attained. The methods also demonstrated precise synthesis of end-functionalized polymers that showed unique optical properties combined with the end groups. Catalytic one-pot syntheses of end-functionalized poly(9,9-dialkylfluorene-2,7-vinylene)s have been attained by both ruthenium (by chain-transfer) and molybdenum catalysts and the method should provide more green route for synthesis of conjugated materials with better device performance.

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Synthesis of Poly(arylene vinylene)s with Different End Groups by Combining Acyclic Diene Metathesis Polymerization with Wittig‐type Couplings

et al. 2017

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As eries of end-functionalized poly(9,9'-di-n-octylfluorene vinylene)s (EF-PFVs) with different end groups were obtained by 1) synthesizing EF-PFV with vinyl end groups by acyclic diene metathesis (ADMET) polymerization with am olybdenum catalyst and termination with an aldehyde and 2) subsequent olefin metathesis of the vinyl group with the molybdenum catalyst followed by Wittig-type coupling with another aldehyde.T he exclusive formation of EF-PFVs containing av inyl end group by the ADMET polymerization was confirmed by grafting PEG,a nd by the synthesis of amphiphilic triblock copolymers by combining atom transfer radical polymerization from the PFV chain end with PEG grafting through ac lick reaction. Various EF-PFVs with different end groups,s uch as C 6 F 5 ,p yridyl, ferrocenyl, and terthiophene,h ave thus been prepared. Their fluorescence spectra (e.g., intensities,emission wavelengths) were influenced by the end groups and the length of the conjugation.Conjugated polymers,s uch as poly(para-phenylene), polyfluorene,p oly(para-arylene vinylene)s,a nd polythiophene, are promising organic materials applied in optoelectronic and electrochemical devices. [1,2] Theprecise,efficient synthesis of defect-free (regular structures,c hemically pure) end-functionalized conjugated polymers has attracted considerable attention, not only for improving device performance, [2] but also because of the unique (optical and/or electronic) properties that result from the end modification (e.g., by energy transfer), as recently demonstrated for polyfluorenes containing discrete end groups,s uch as triarylamines,p erylene monoimide dyes,o rh eteroaryl moieties, [3][4][5] and poly(9,9dialkylfluorene-2,7-vinylene)s (PFVs). [6,7] It has been demonstrated that syntheses by acyclic diene metathesis (ADMET) polymerization [6][7][8][9][10][11] afford defect-free (without halogen/sulfur impurities,r egio-or stereoirregularity,orcross-linking etc.)PFVs, [6][7][8] poly(2,5-dialkylphenylene-1,4-vinylene)s, [9] and poly(N-alkylcarbazole-2,7-vinylene)s [8b] that display better properties than those prepared by conventional condensation (e.g., dehalogenation-condensation, Gilch reaction) methods.M oreover,e xclusive end functionalization can be achieved by treating the vinyl end groups in the resultant polymers prepared with ar uthenium carbene catalyst [6, 8b, 9] with Mo(CHCMe 2 Ph)(N-2,6-Me 2 C 6 H 3 )[OC-(CH 3 )(CF 3 ) 2 ]( "Mo catalyst") followed by Wittig-type coupling with an aldehyde. [12,13] One-pot approaches for combined ADMET polymerization and subsequent end functionalization with Ru [7a] and Mo [7b] catalysts have also recently been established. These methods,h owever,o nly provide synthetic means to introduce the same functional groups at the PFV chain ends,and precise methods for the synthesis of well-defined poly(arylene vinylene)s containing different end groups have been limited thus far.W eh erein report that different end groups can be introduced at PFV chain ends by combining ADMET polymerization with the Mo catalys...

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Precise One-Pot Synthesis of End-Functionalized Conjugated Multi-Block Copolymers via Combined Olefin Metathesis and Wittig-type Coupling

Cited by 30 publications

References 86 publications

Acyclic Diene Metathesis (ADMET) Polymerization for Precise Synthesis of Defect-Free Conjugated Polymers with Well-Defined Chain Ends

Acyclic Diene Metathesis (ADMET) Polymerization for Precise Synthesis of Defect-Free Conjugated Polymers with Well-Defined Chain Ends

ADMET Polymerization: Greener Method for Synthesis of End-Functionalized Poly(Arylene Vinylene)s

Synthesis of Poly(arylene vinylene)s with Different End Groups by Combining Acyclic Diene Metathesis Polymerization with Wittig‐type Couplings

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