Synthesis and optical properties of water-soluble diketopyrrolopyrroles

Grzybowski, Marek; Głodkowska-Mrówka, Eliza; Clermont, Guillame; Blanchard‐Desce, Mireille; Gryko, Daniel T.

doi:10.1007/s10593-017-2023-y

“…The first endeavor of this work focused on the synthesis of isoindoledione 2 (selected due to its bathochromically shifted emission among the reported series) [8] andi ts transformation into the water-soluble derivative 4.D iketopyrrolopyrrole (DPP) 1 possessing two benzofuryl groups was treated with trimethylsilyl bromide and hydroxyl(tosyloxy)iodobenzene (HTIB) in HFIP,l eadingt or ing rearrangement and formation of dye 2 (Scheme 1). Typically,i onic functional groups, such as quaternary ammonium cations, are introduced to non-polarizable chromophores to increase their water solubility.T hus, our initial strategy was based on the reaction of the parent isoindoledione 2 with (3-bromopropyl)triethylammonium bromide under the conditions that avoid self-alkylation [11] of the alkylating agent (NaH, DMF,4 0 8C). Unfortunately,t he alkylation of dye 2 afforded ac omplex,i nseparable mixture of polar products despite the different ratios of reagents used.…”

Section: Design and Synthesismentioning

confidence: 99%

Modified Isoindolediones as Bright Fluorescent Probes for Cell and Tissue Imaging

Vakuliuk

¹

,

Jun

²

,

Vygranenko

³

et al. 2019

Chemistry A European J

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New L‐shaped fluorophores possessing five conjugated rings have been synthesized through a four‐step procedure involving diketopyrrolopyrrole synthesis and its double N‐alkylation, followed by trimethylsilyl bromide‐mediated rearrangement to thieno[2,3‐f]isoindole‐5,8‐dione and an intramolecular Friedel–Crafts reaction. In comparison with the parent isoindolediones and π‐expanded diketopyrrolopyrroles, these new dyes show red‐shifted absorption and emission (up to ≈630 nm). Their structural rigidity is responsible for both the observed small Stokes shifts and large fluorescence quantum yields. Tissue imaging studies revealed that these new dyes show advantageous features including minimal autofluorescence interference and pronounced solvent‐sensitive emission. Interestingly, there is a fundamental difference between a dye possessing an amino group and its analog bearing an N‐alkyl substituent. The former dye under two‐photon excitation at 900 nm gives bright images whereas its N‐alkylated counterpart does not. A new type of membrane localization has been discovered by an N‐alkylated isoindoledione possessing a benzofuryl substituent. In spite of the fact that the fluorescence quantum yield of this dye in a range of solvents is rather low, it does stain cell membranes exclusively. This new mode of cellular staining opens the door towards further development of membrane staining dyes.

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“…It has been well established that the intramolecular hydrogen bonding in the DPP compounds hinders its solubility in any kind of solvent. In order to have the DPP compounds solvated in water their polarity needs to be enhanced by the addition of ionic functional groups, 47 or in some cases also by carboxylic acid functional groups. 48 The absence of any such functional groups in the simulated polymers leads to the low solubility in water.…”

Section: B Np-dpp2pymt In Solutionmentioning

confidence: 99%

Development and Testing of an All-Atom Force Field for Diketopyrrolopyrrole Polymers with Conjugated Substituents

Sundaram¹,

Lyulin²,

Baumeier³

2020

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0

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We develop an all-atom force field for a series of diketopyrrolopyrrole polymers with two aromatic pyridine substituents and variable number of pi-conjugated thiophene units in the backbone, used as donor material in organic photovoltaic devices. Available intra-fragment parameterizations of the individual fragment building blocks are combined with inter-fragment bonded and non-bonded parameters explicitly derived from density-functional theory calculations. To validate the force field we perform classical molecular dynamics simulations of single polymer chains with 1, 2, and 3 thiophenes in good and bad solvents, and of melts. We observe the expected dependence of the chain conformation on the solvent quality, with the chain collapsing in water, and swelling in chloroform. The glass transition temperature for the polymer melts is found to be in the range of 340K to 370K. Analysis of the mobility of the conjugated segments in the polymer backbone reveals two relaxation processes: a fast one with a characteristic time at room temperature on the order of 10ps associated with nearly harmonic vibrations and a slow one on the order of 100 associated with temperature activated cis-trans transitions.

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“…It has been well established that the intramolecular hydrogen bonding in the DPP compounds hinders its solubility in any kind of solvent. In order to have the DPP compounds solvated in water their polarity needs to be enhanced by the addition of ionic functional groups, 51 or in some cases also by carboxylic acid functional groups. well represented by the radius of gyration, R g , in water and chloroform.…”

Section: N P -Dpp2pymt In Solutionmentioning

confidence: 99%

Development and Testing of an All-Atom Force Field for Diketopyrrolopyrrole Polymers with Conjugated Substituents

Sundaram¹,

Lyulin²,

Baumeier³

2020

Preprint

0

View full text Add to dashboard Cite

We develop an all-atom force field for a series of diketopyrrolopyrrole polymers with two aromatic pyridine substituents and variable number of pi-conjugated thiophene units in the backbone, used as donor material in organic photovoltaic devices. Available intra-fragment parameterizations of the individual fragment building blocks are combined with inter-fragment bonded and non-bonded parameters explicitly derived from density-functional theory calculations. To validate the force field we perform classical molecular dynamics simulations of single polymer chains with 1, 2, and 3 thiophenes in good and bad solvents, and of melts. We observe the expected dependence of the chain conformation on the solvent quality, with the chain collapsing in water, and swelling in chloroform. The glass transition temperature for the polymer melts is found to be in the range of 340K to 370K. Analysis of the mobility of the conjugated segments in the polymer backbone reveals two relaxation processes: a fast one with a characteristic time at room temperature on the order of 10ps associated with nearly harmonic vibrations and a slow one on the order of 100 associated with temperature activated cis-trans transitions.

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Synthesis and optical properties of water-soluble diketopyrrolopyrroles

Cited by 11 publications

References 10 publications

Modified Isoindolediones as Bright Fluorescent Probes for Cell and Tissue Imaging

Modified Isoindolediones as Bright Fluorescent Probes for Cell and Tissue Imaging

Development and Testing of an All-Atom Force Field for Diketopyrrolopyrrole Polymers with Conjugated Substituents

Development and Testing of an All-Atom Force Field for Diketopyrrolopyrrole Polymers with Conjugated Substituents

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