Negishi coupling in the synthesis of advanced electronic, optical, electrochemical, and magnetic materials

Huo, Shouquan; Mroz, Robert; Carroll, Jeffrey

doi:10.1039/c4qo00322e

Cited by 36 publications

(20 citation statements)

References 195 publications

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“…The high interest in these materials is owed to their outstanding properties, such as high absorbance coefficients, good charge carrier mobility, high fluorescence quantum yields, and ease of processability—all while having tunable properties through structural variation. However, methods developed for poly(hetero)arene preparation are mainly limited to transition‐metal‐catalyzed coupling methods, such as the Stille coupling, Suzuki coupling, Kumada coupling, Negishi coupling, and direct arylation (Figure A) . Although the available methods have proven to be indispensable for exploring of the applications of poly(hetero)arene conjugated polymers, one or more drawbacks can hamper their synthetic utility, that is, the use of relatively expensive catalysts, residual transition metal impurities, synthetically complex monomers, hazardous organometallic intermediates, and toxic waste streams.…”

Section: Figurementioning

confidence: 99%

Dehydration Polymerization for Poly(hetero)arene Conjugated Polymers

Mirabal

Vanderzwet

Abuadas

et al. 2018

Chemistry A European J

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The lack of scalable and sustainable methods to prepare conjugated polymers belies their importance in many enabling technologies. Accessing high-performance poly(hetero)arene conjugated polymers by dehydration has remained an unsolved problem in synthetic chemistry and has historically required transitional-metal coupling reactions. Herein, we report a dehydration method that allows access to conjugated heterocyclic materials. By using the technique, we have prepared a series of small molecules and polymers. The reaction avoids using transition metals, proceeds at room temperature, the only required reactant is a simple base and water is the sole by-product. The dehydration reaction is technically simple and provides a sustainable and straightforward method to prepare conjugated heteroarene motifs.

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Section: Figurementioning

confidence: 99%

Dehydration Polymerization for Poly(hetero)arene Conjugated Polymers

Mirabal

Vanderzwet

Abuadas

et al. 2018

Chemistry A European J

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“…Whilst cross‐coupling reactions using stannanes are prominent in the synthesis of thienyl D –A systems due to their reliability, drawbacks exist particularly associated with the toxicity of organostannane compounds. Negishi cross‐coupling reactions utilise nontoxic and highly nucleophilic organozinc reagents . The application of Negishi cross‐coupling to 1‐BPh 2 using a previously reported zincate as the transmetalation reagent results in the formation of 6‐BPh 2 in an excellent isolated yield (98 %) with the workup a simple filtration through silica gel (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

“…Negishi cross-coupling reactions utilise nontoxic and highly nucleophilic organozinc reagents. [13] The application of Negishic ross-coupling to 1-BPh 2 using ap reviously reported zincate as the transmetalation reagent [14] results in the formation of 6-BPh 2 in an excellent isolated yield (98 %) with the workup as imple filtration through silica gel (Scheme 3). This material is not studied further herein as its band-gap will be larger than that of 2-BPh 2 based on ptolyl being aw eaker donor moiety than F8, but it does confirm that Negishi protocols are compatible with the borylated moiety.…”

Section: Resultsmentioning

confidence: 99%

“…The reaction mixture was stirred for 2h," wet" toluene (unpurified toluene used as received;1 0mL) was added to the reaction mixture which was then passed through ap lug of silica. The resulting solution was purified by silica-gel chromatography (5 %N Et 3 in hexane; eluent:h exane/DCM 9:1) to afford the desired product as ad ark 1, 147.8, 142.4, 140.7, 135.3, 133.6, 130.1, 128.9, 127.6, 127.4, 126.7, 126.1, 125.8, 123.5, 122.7, 120.6, 116.4, 110.5, 54.8, 40.6, 31.7, 30.0, 29.2, 29.1, 23.9, 22.5, 14. 13 Synthesis of 5-B(C 6 F 5 ) 2 :C ompound 1-B(C 6 F 5 ) 2 (150 mg, 0.16 mmol), 2,5-bis(tri-n-butylstannyl)thieno[3,2-b]thiophene (56 mg, 0.08 mmol) and Pd(PPh 3 ) 4 (17 mg, 0.016 mmol) was dissolved in toluene (4 mL) and heated at 100 8Cf or 40 h. After evaporating the solvent, the residue was purified by column chromatography on silica gel (eluent:h exane/DCM 6:4) to afford 5-B(C 6 F 5 ) 2 as ad ark green residue (yield 51 mg, 35 %). 1 Synthesis of 6-BPh 2 :C ompound 1-BPh 2 (50 mg, 0.065 mmol), zincate (75 mg, 0.078), [Pd 2 (dba) 3 ]( 3.5 mg, 0.004 mmol) and S-Phos (5.3 mg, 0.013 mmol) were dissolved in THF (3 mL).…”

Section: Synthesis and Characterisationmentioning

confidence: 99%

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Highly Emissive Far Red/Near‐IR Fluorophores Based on Borylated Fluorene–Benzothiadiazole Donor–Acceptor Materials

Crossley

Vitórica-Yrezábal

Humphries³

et al. 2016

Chemistry A European J

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Stille, Suzuki-Miyaura and Negishi cross-coupling reactions of bromine-functionalised borylated precursors enable the facile, high yielding, synthesis of borylated donor-acceptorm aterialst hat contain electron-rich aromatic units and/or extendede ffective conjugation lengths. These materials have large Stokes shifts, low LUMO energies, small band-gapsa nd significant fluorescencee mission > 700 nm in solution and when dispersed in ahost polymer. IntroductionNear-infrared (NIR) absorbing ande missive molecules have attracted significanti nterest due to potential applications including night-vison displays, sensors and in-vivo imaging. [1,2] Generating organic NIR emitters that have appreciable quantum yields is challenging due to the energy gap law where the emission efficiency reduces with decreasing energy gap. [3] This is exacerbated in the solid state as aggregation often leads to additionaln on-radiative pathways and significant emission quenching. [4] Onee ffective strategy for accessing low-bandgap materials is to construct p-conjugated systems containing donor (D) and acceptor( A) groups. [5] However, D-A materials with appreciable solid state NIR emissiona re currently rare, [2d] therefore new low-band-gap D-A materials are desirable, particularly if accessible by simple modular routes.Another attractive property of D-A materials is the large degree of controlo ver the electronic and optical properties by rational structural modification.F or example, the coordination of aL ewis acid to aL ewis basic site on an acceptorm oiety has been previously used to generate D-A materials with low LUMO energies and small band-gaps. [6] Ar elated approach that generates D-A materials that are more stable to moisture and Lewis bases appendsB R 2 moietiest oac onjugated framework throughf ormationo faC ÀBb ond and ad ative bond from the acceptor to the boronc entre. [7] We have recently utilised this methodology to synthesise borylated 9,9-dioctylfluorene-benzothiadiazole (F8-BT)c ontaining D-A materials by directedelectrophilicb orylation which concomitantly formsaCBa nd aN !Bb ond. [8] This borylation reactionp lanarises the conjugated backboneg eneratingr igid structures with extended effective conjugation lengths.T hese fused materials showed large Stokes shifts, low band-gaps, were stable to H 2 O and O 2 and wereh ighly emissive in solution and the solid state;f or example, F8-BT-F8 functionalised with aB Ph 2 group was highly emissive in the solid state (PLQY3 3% with l max = 696 nm). [8] Whilst notable it is desirable to develop synthetic routest or apidly access analogues with lower band-gapst hat were highly emissive in the solids tate with emissionf urther into the NIR (l max @ 700 nm).As imple approacht od eliver these materials is to introduce more electron-rich donor units than F8 and/or to extend the effective conjugation length.H owever,c oupling other donor units to F8-BT generates unsymmetric F8-BT-D materials that complicates the electrophilic borylation step, particularly wheree lectr...

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“…The reaction has been the focus of study for over5 0years, due to the synthetic importanceo ft hesec ompounds in Negishic ross-coupling and other CÀCb ondf orming reactions. [6][7][8][9][10][11] Initially,p olar aprotics olvents (e.g.,m ixtures with DMSO, [12,13] or DMF [7,14] ) were required. This requirement was circumventedl ater by Knochel, who showedt hat LiCl salt additive enabled direct in-sertioninTHF.…”

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confidence: 99%