Expanding the Scope of Electron-Deficient C–H Building Blocks: Direct Arylation of Pyromellitic Acid Diimide

Hameury, Sophie; Kunz, Susanna V.; Sommer, Michael

doi:10.1021/acsomega.7b00420

Cited by 23 publications

(19 citation statements)

References 45 publications

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“…[17] According to recent studies, am ore stable Buchwald catalyst generation three (Pd 2 G 3 )w as found to be ag ood alternative to Pd 2 (dba) 3 in DA. [18,19] Indeed, as imilar result was observed with Pd 2 G 3 ( Table 1, entry 6). We thus used Pd 2 G 3 as catalysti na ll followinge ntries for the sake of abetter reproducibility.…”

supporting

confidence: 76%

“…It is important to note that we here used commercial and stored Pd 2 (dba) 3 , which is known to generate Pd nanoparticles during storage and thus potentially affect reaction reproducibility . According to recent studies, a more stable Buchwald catalyst generation three (Pd 2 G 3 ) was found to be a good alternative to Pd 2 (dba) 3 in DA . Indeed, a similar result was observed with Pd 2 G 3 (Table , entry 6).…”

Section: Methodssupporting

confidence: 60%

“…Importantly,w hen DA is applied to the synthesis of p-conjugated electronic materials,f rom slight to largelye xcess stoichiometric ratios have unfortunately been neededt oa chieve high yields by suppressing side reactions. [9,12,18,20] However,t he mono-functionality of NTI [21] and the high efficiencyo fh erein optimized DA protocol allowed for an exact stoichiometryb etween reactants.…”

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confidence: 99%

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Synthesis of Thiophene‐annulated Naphthalene Diimide‐based Small‐Molecular Acceptors via Two‐step C−H Activation

Matsidik

Takimiya

2019

Chemistry An Asian Journal

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Thiophene-annulated naphthalene diimide (NTI)-based molecules have recently emerged as an important class of n-type electronic materials. However,t heir synthesis has predominantly been achieved by Stille or Suzuki coupling reactions despite the presence of ap otential CÀHb ond in NTI. Additionally,t he synthesis of NTI or more generally mono-functionalizationo fn aphthalene diimide (NDI) starts with ac umbersome bromination that results in al ow yield, is unselective, and requires tedious purification. Weh erein thus addresst hese issues via a two-step CÀHa ctivation:arhodium-catalyzed direct CÀH iodinization is first presented for NDI, followed by establishing an efficient direct arylation protocol for NTI with high yield and robustness. Coupling of up to four NTI units on ab enzene or pyrene core is demonstrated along with other aryl bromide substrates. Allt he herein reported NTI-based small molecules showed n-type semiconductor behavior under air. 1,4,5,8-Naphthalenetetracarboxylic diimide is the smallest member in the class of rylene diimides. Due to its uniqueproperties, such as ease of structural modification,e lectron deficient and planars tructure, high electron mobility and unconventional morphological behavior,N DI has become one of the most versatile and widely studied skeletons. [1][2][3] NDI-derived materials thus play an important role in research fields ranging from supramolecular chemistry,e lectron transfer systems, to organic electronics. [4,5] In the course of NDI-based materials for organic electronics, p-extension of NDIc ore through ringfusion at its four a-positions or coupling through its 2,6-positions has been aw idely applied strategy to control opto/electronic properties. [1][2][3] Nevertheless, mono-functionalization of the NDI core has received lessa ttention due to synthetic difficulties resulting from as imilar reactivity of the a-positions on the NDI core, despitei ts potential to further extend the material scope of NDI-based opto/electronics tructures. [6,7] We recently reported am ono-thiophene-fused NDI, namely naphtho[2,3-b]thiophene diimide( NTI), [6] which was then applied to generatev ariousN TI-terminated p-conjugated architectures that showed excellent n-type performance in organic electronics, demonstrating its potential as av ersatile building block. [6,8] However,t he synthesis of these NTI-terminated structures has been achieved to date by conventional coupling techniques such as Stille or Suzuki cross-coupling reactions, [6,8] while ad irect arylation (DA) protocol has recently been reported fors ymmetric thiophene-annulated NDI. [9] Indeed, the CÀH bond at the a-position of thiophene on NTI holds ag reat potential to be used in DA, in which NTI can be directlyc oupled with halogenated substrates, making the bromination of NTI and prefuctionalization to generate reactive organometallic substrates that are necessary in other coupling reactions redundant. [10][11][12] Thus, developing an efficient CÀHa ctivation protocol fort he NTI unit not only reduces synthetic st...

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supporting

confidence: 76%

Section: Methodssupporting

confidence: 60%

mentioning

confidence: 99%

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Synthesis of Thiophene‐annulated Naphthalene Diimide‐based Small‐Molecular Acceptors via Two‐step C−H Activation

Matsidik

Takimiya

2019

Chemistry An Asian Journal

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“…This method has gained considerable recent momentum as a significantly environmentally and economically attractive alternative to classical cross-coupling such as Suzuki-Miyaura, Negishi, and Stille reactions [6][7][8][9][10]. With fewer steps and accessible reagents, complex organic molecules are nowadays easily accessible with C-H activation [11][12][13][14][15][16][17][18][19][20]. Nevertheless, this reaction usually requires high temperatures and organic solvents to achieve new C(sp 2 )-C(sp 2 ) bonds [21].…”

Section: Introductionmentioning

confidence: 99%

“On Water” Palladium Catalyzed Direct Arylation of 1H-Indazole and 1H-7-Azaindazole

et al. 2020

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The C3 direct arylation of 1H-indazole and 1H-7-azaindazole has been a significant challenge due to the lack of the reactivity at this position. In this paper, we describe a mild and an efficient synthesis of new series of C3-aryled 1H-indazoles and C3-aryled 1H-7-azaindazoles via a C3 direct arylation using water as solvent. On water, PPh3 was effective as a ligand along with a lower charge of the catalyst Pd(OAc)2 (5 mol%) at 100 °C, leading to C3-aryled 1H-indazoles or C3-aryled 1H-7-azaindazoles in moderate to good yields.

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“… 15 − 18 The smallest of aromatic diimides, pyromellitic diimide (PMDI), has received significantly less attention in these areas than the larger naphthalene and perylene diimides despite exhibiting promising behavior in electronic settings 14 , 19 alongside interesting absorption and emission characteristics. 9 , 20 Explanations for this disparity often point to the challenge of incorporating functionalities at the PMDI core positions 21 and the more negative voltages required by PMDI-based redox systems to reach their reduced states. 11 , 22 With these perceived limitations in mind, we sought to demonstrate a molecular design that leads to significant shifts of PMDI reduction potentials toward more positive voltages.…”

Section: Introductionmentioning

confidence: 99%

Pyridinium-Functionalized Pyromellitic Diimides with Stabilized Radical Anion States

et al. 2018

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In this work, we report the stabilization of the reduced states of pyromellitic diimide by charge-balancing the imide radical anions with cationic pyridinium groups attached to the aromatic core. This structural modification is confirmed by single-crystal X-ray diffraction analysis. Characterization by (spectro)electrochemical experiments and computations reveal that the addition of cationic groups to an already electron-deficient ring system results in up to +0.57 V shifts in reduction potentials, largely as a consequence of charge screening and lowest unoccupied molecular orbital-lowering effects. This formal charge-balancing approach to stabilizing the reduced states of electron-deficient pyromellitic diimides will facilitate their incorporation into spin-based optoelectronic materials and devices.

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Expanding the Scope of Electron-Deficient C–H Building Blocks: Direct Arylation of Pyromellitic Acid Diimide

Cited by 23 publications

References 45 publications

Synthesis of Thiophene‐annulated Naphthalene Diimide‐based Small‐Molecular Acceptors via Two‐step C−H Activation

Synthesis of Thiophene‐annulated Naphthalene Diimide‐based Small‐Molecular Acceptors via Two‐step C−H Activation

“On Water” Palladium Catalyzed Direct Arylation of 1H-Indazole and 1H-7-Azaindazole

Pyridinium-Functionalized Pyromellitic Diimides with Stabilized Radical Anion States

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