Towards more sustainable synthesis of diketopyrrolopyrroles

Pop, Flavia; Humphreys, Joshua; Schwarz, Jesper; Brown, Louise P.; Berg, Ashmiani van den; Amabilino, David B.

doi:10.1039/c9nj01074b

Cited by 25 publications

(28 citation statements)

References 55 publications

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“…For instance, the reactions were performed under microwave irradiation as the heating source. In a first attempt, the reaction was carried out at room temperature to slow the formation of sub‐products, since at high temperature and basic conditions, both N‐ and O‐alkylation are favored . After 1 hour, only the mono N ‐alkylated product was obtained together with unreacted DPP and mesylate.…”

Section: Resultsmentioning

confidence: 99%

Impact of Chirality on Hydrogen‐Bonded Supramolecular Assemblies and Photoconductivity of Diketopyrrolopyrrole Derivatives

Militzer

Nishimura

Ávila‐Rovelo

et al. 2020

Chemistry A European J

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Hydrogen bonds can efficiently guide the self-assembly of organic materials, enabling to tune the properties of the aggregation processes. In the case of p-conjugated materials, several parameters such as temperature, concentration and solvent can be used to modify the aggregation state while tuning the optoelectronic properties. Chirality can be included within the impacting parameters due to the differences in molecular packing. Here, chiral and achiral thiophene-capped diketopyrrolopyrrole derivatives were designed and synthesized containing amide bonds, with the aim to study the interplay between chiral assemblies and their stabilization throughh ydrogen-bonding. Differences in aggregation properties were observed with spectroscopy and microscopy,a nd ac ontactless microwave-based technique was used to study their intrinsic chargec arrierm obility.T he positive role of hydrogen-bonding has been highlighted and the differences between chiral and achiral compoundsh ave been elucidated.

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Section: Resultsmentioning

confidence: 99%

Impact of Chirality on Hydrogen‐Bonded Supramolecular Assemblies and Photoconductivity of Diketopyrrolopyrrole Derivatives

Militzer

Nishimura

Ávila‐Rovelo

et al. 2020

Chemistry A European J

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“…Product purification was done by means of column chromatography with Kieselgel 60. The identity and purity of the prepared compounds were proven by 1 H NMR, 13 C NMR, spectrometry as well as mass spectrometry (via EI-MS or ESI-MS). HRMS (ESI-TOF) and HRMS (EI): double-focusing magnetic sector instruments with EBE geometry were utilized.…”

Section: Experimental Section General Remarksmentioning

confidence: 99%

“…[12] One of the most common modifications of DPPs is N-alkylation which is performed in polar aprotic media in the presence of base. [13] Unlike the ubiquitous N-alkylation, N-arylation of DPPs remains a formidable challenge due to the lack of synthetic methods and therefore these derivatives are relatively exotic. One of the synthetic pathways relies on the condensation between poorly accessible diphenyl -1,4-dihydrofuro-[3,4-c] furan-1,4-dione and a corresponding aniline in the presence of DCC.…”

Section: Introductionmentioning

confidence: 99%

“…Further investigation proved that functionalization of the nitrogen atom of the lactam ring increases solubility and enhances the optical properties making them very useful functional dyes . One of the most common modifications of DPPs is N ‐alkylation which is performed in polar aprotic media in the presence of base . Unlike the ubiquitous N ‐alkylation, N ‐arylation of DPPs remains a formidable challenge due to the lack of synthetic methods and therefore these derivatives are relatively exotic.…”

Section: Introductionmentioning

confidence: 99%

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N‐Arylation of Diketopyrrolopyrroles with Aryl Triflates

Gutkowski

Skonieczny

Bugaj

et al. 2020

Chemistry An Asian Journal

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A new methodology for the double N-arylation of diketopyrrolopyrroles with aryl triflates has been developed. It is now possible to prepare diketopyrrolopyrroles bearing Nsubstituents derived from naphthalene, anthracene and coumarin in two steps from commercially available phenols. This represents the first time arenes lacking strong electronwithdrawing groups were inserted onto lactamic nitrogen atoms via arylation. The ability to incorporate heretofore unprecedented substituents translates to increased modulation of the resulting photophysical properties such as switching-on/off solvatofluorochromism. TD-DFT calculations have been performed to explore the nature of the relevant excited states. This new synthetic method made it possible to elucidate the influence of such substituents on the absorption and emission properties of tetraaryl substituted diketopyrrolopyrroles.

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“…Synthesis of the parent DPPs was carried out according to literature procedures and N ‐alkylation of these compounds was carried out using standard or more efficient conditions giving the target compounds in moderate yields (similar to related compounds of this type) after purification (55 % 4MB ThDPP, 57 % 4MB OMePhDPP, 40 % 4MB ThPhDPP). This structural modification facilitates solubility of the DPPs in common organic solvents, allowing for detailed structural and electronic characterization (see Supporting Information).…”

Section: Resultsmentioning

confidence: 99%

Ground and Excited States of Bis‐4‐Methoxybenzyl‐Substituted Diketopyrrolopyrroles: Spectroscopic and Electrochemical Studies

et al. 2019

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A series of symmetrically bis‐4‐methoxybenzyl (4MB) N‐substituted 1,4‐diketopyrrolo[3,4‐c]pyrrole (DPP) derivatives have been synthesized. The 4MB unit makes the DPP core soluble, and shows subtle modification of up to 0.2 eV in ground and excited states of the core when compared with related alkyl derivatives. Absorption and emission spectroscopy, as well as electrochemical and computational methods have been employed to prove the importance of the peripheral aryl units on the donor/ acceptor properties of the molecules. The 4MB products are highly fluorescent (quantum yields approaching 100 % in solution), with a unique distribution of frontier states shown by spectroelectrochemistry. The solid‐state fluorescence correlates with the X‐ray crystal structures of the compounds, a Stokes shift of approximately 80 nm is seen for two of the compounds. The frontier energy levels show that this subtle substitutional change could be of future use in molecular energy level tailoring in these, and related, materials for organic (opto)electronics.

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Towards more sustainable synthesis of diketopyrrolopyrroles

Abstract: Functionalisation of diketopyrrolopyrroles with improved energy use during synthesis, ease of isolation, and yields of reactions is reported.

Cited by 25 publications

References 55 publications

Impact of Chirality on Hydrogen‐Bonded Supramolecular Assemblies and Photoconductivity of Diketopyrrolopyrrole Derivatives

Impact of Chirality on Hydrogen‐Bonded Supramolecular Assemblies and Photoconductivity of Diketopyrrolopyrrole Derivatives

N‐Arylation of Diketopyrrolopyrroles with Aryl Triflates

Ground and Excited States of Bis‐4‐Methoxybenzyl‐Substituted Diketopyrrolopyrroles: Spectroscopic and Electrochemical Studies

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