Synthetic studies related to diketopyrrolopyrrole (DPP) pigments. Part 2: The use of esters in place of nitriles in standard DPP syntheses: Claisen-type acylations and furopyrrole intermediates

Morton, Colin; Riggs, R.L.; Smith, David M.; Westwood, Nicholas J.; Lightfoot, Philip; Slawin, Alexandra M. Z.

doi:10.1016/j.tet.2004.10.027

Cited by 32 publications

(14 citation statements)

References 6 publications

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“…However, in the literature, asymmetrical DPPs are obtained almost exclusively from lactams of type 8' . [ 18 ] This can probably be explained by the better stability of compound 8' relative to 7' , which contains a sensitive enamine unit. Additionally, the synthesis of compound 8' through the alkylation of β -ketoester 13 and cyclization seems to be easier to perform than the preparation of 7' by the addition of succinate to nitrile in the presence of an excess of lithium diisopropylamide (LDA).…”

Section: Reviewmentioning

confidence: 99%

Diketopyrrolopyrroles: Synthesis, Reactivity, and Optical Properties

Grzybowski

Gryko

2015

Advanced Optical Materials

340

293

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First reported by Farnum as much as 40 years ago, diketopyrrolopyrroles (2,5‐dihydropyrrolo[4,3‐c]pyrrolo‐1,4‐diones) are currently one of the most widely used dyes, with applications that span high‐quality pigments, field‐effect transistors, bulk‐heterojunction solar cells, dye‐sensitized solar cells, and fluorescence imaging. Due to the breadth of their utility, there have been several focused reviews on this topic since 1988. Considering the growing importance of these dyes, this review describes the overall progress made in four decades in both synthesis and the elucidation of their reactivity, and offers a critical comparison of various methods reported in the literature. The relationship between their structure and optical properties is also reviewed in detail. The extension of diketopyrrolopyrroles' chromophore leads to a significant change in both linear and nonlinear optical properties. A very strong bathochromic shift in the absorption and an increase in the two‐photon absorption cross‐section are typical for these analogues. Straightforward synthesis combined with good stability and a near‐unity fluorescence quantum yield ensures that diketopyrrolopyrroles will continue to attract attention for years to come. The goal of this review is to systematize knowledge on these dyes, enabling their use in more real‐world applications.

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Section: Reviewmentioning

confidence: 99%

Diketopyrrolopyrroles: Synthesis, Reactivity, and Optical Properties

Grzybowski

Gryko

2015

Advanced Optical Materials

340

293

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“…Syntheses of the small molecules were achieved through Suzuki or Stille cross‐coupling reactions to append the end‐groups to the DPP core (see Supporting Information, SI) 3, 11. Notably, the C2‐pyrene boronate ester was obtained by Ir(I)‐ catalyzed C‐H functionalization for selective access to the C2 position 12.…”

Section: Average Pv Performance Of 1–4 Blended With Pc71bmmentioning

confidence: 99%

Efficient Small Molecule Bulk Heterojunction Solar Cells with High Fill Factors via Pyrene‐Directed Molecular Self‐Assembly

et al. 2011

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Efficient organic photovoltaic (OPV) materials are constructed by attaching completely planar, symmetric end-groups to donor-acceptor electroactive small molecules. Appending C2-pyrene as the small molecule end-group to a diketopyrrolopyrrole core leads to materials with a tight, aligned crystal packing and favorable morphology dictated by π-π interactions, resulting in high power conversion efficiencies and high fill factors. The use of end-groups to direct molecular self-assembly is an effective strategy for designing high-performance small molecule OPV devices.

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“…Among the different synthetic routes to the DPP moiety [104][105][106][107][108] , the most commonly employed method uses aromatic nitriles with a succinic ester in the presence of a strong base 104,109 and this was selected for the synthesis of the series, of the compounds described in this thesis. The first step in the synthesis of DPP core with two thiophenes attached was therefore the formation of the 2-cyanothiophene 2.6, and two routes were investigated (Scheme 2.1).…”

Section: Synthesis Of Dpp(th) 2 With 2-ethylhexyl Solubilising Groupsmentioning

confidence: 99%

Low optical gap materials for organic solar cells - research and application

Chandrasekharan¹

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In spite of the cost of silicon solar cells decreasing in recent years, there is considerable interest in solar cells with lightweight and flexible forms. Organic semiconductor-based photovoltaic cells (OPVs) have the potential to offer low cost, lightweight and flexible devices. At this stage there is still much to be improved for OPVs as the efficiencies are still lower than their inorganic counterparts. Polymeric materials have been more widely studied than their non-polymeric counterparts. In recent years OPVs polymeric donor materials have emerged with efficiencies reaching 10% with quite a range of materials now providing efficiencies of around 7%. However, the problem with semiconducting polymers is that control of the regioregularity, poly(dispersity), and molecular weight from batch-to-batch is not a simple process. Solution-processable nonpolymeric semiconductors are attractive for opto-electronic applications as they are simpler to synthesise, purify, characterise, and the optical properties can be more easily fine-tuned. In this context, diketopyrrolopyrrole (DPP) based small molecules have shown promising results with devices efficiencies reaching around 5-6%. Key properties of the DPP unit are strong π-π interactions, and suitable and tunable energy levels. These properties have been the main drivers in their use in OPVs.This thesis consist of the synthesis, characterisation, and bulk hetrojunction (BHJ) devices properties of novel DPP(ThAr) 2 non-polymeric materials. Accordingly, a first series of compounds was synthesized with different electron affinity groups such as fluorenone (Fl) [EhDPP(ThFl) 2 and OddDPP(ThFl) 2 ] and benzothiadiazole (Bt) [OddDPP(ThBt) 2 ] attached to the distal ends of a bisthienyl-diketopyrrolopyrrole unit DPP(Th) 2 unit. The 'DPP(ThAr) 2 ' derivatives were synthesised under standard Suzuki-Miyaura cross-coupling or by direct arylation reaction conditions and the rate of the direct arylation reaction was found to be faster than for the Suzuki-Miyaura crosscoupling reactions. The solubility of the compounds was poor when the 2-ethylhexyl (Eh) moiety was used as the solubilising group for DPP(ThFl) 2 . 2-Octyldodecyl (Odd) solubilising groups gave better solubility in chlorinated solvents, which are typically used in OPV fabrication. The three nonpolymeric DPP materials exhibited bipolar charge transport in organic field effect transistors (OFETs), with hole and electron mobility in the order of 10 -2 −10 -3 cm 2 V -1 s -1 , and in a diode architecture OddDPP(ThFl) 2 and OddDPP(ThBt) 2 exhibited mobilities of the order of 10 -4 cm 2 V -1 s -1 for pristine films. In BHJ devices using [6,6]-phenyl-C70-butyric acid methyl ester (PC70BM)as the acceptor, different solvent mixtures were used for device fabrication to achieve the maximum efficiency. The EQE spectra of the blend film suggested that charge generation due to absorption at iii wavelengths longer than 750 nm occurred through the Channel I pathway, and at wavelengths shorter than 750 nm, both Channel I and II ...

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Synthetic studies related to diketopyrrolopyrrole (DPP) pigments. Part 2: The use of esters in place of nitriles in standard DPP syntheses: Claisen-type acylations and furopyrrole intermediates

Cited by 32 publications

References 6 publications

Diketopyrrolopyrroles: Synthesis, Reactivity, and Optical Properties

Diketopyrrolopyrroles: Synthesis, Reactivity, and Optical Properties

Efficient Small Molecule Bulk Heterojunction Solar Cells with High Fill Factors via Pyrene‐Directed Molecular Self‐Assembly

Low optical gap materials for organic solar cells - research and application

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