The impact of interplay between electronic and steric effects on the synthesis and the linear and non-linear optical properties of diketopyrrolopyrrole bearing benzofuran moieties

Anna Purc, Beata Koszarna, Irina Iachina, Daniel H. Friese, Mariusz Tasior, Krzysztof Sobczyk, Tomasz Pȩdziński, Jonathan Brewer, Daniel T. Gryko*

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Resumé

An in-depth investigation of the reaction of substituted salicylaldehydes with chloroacetonitrile led to the development of new conditions for the synthesis of 2-cyanobenzofurans. The crucial improvement lies in the use of phase-transfer catalysis in the second step, i.e., intramolecular aldol type condensation. In a two-step process, the reactants were transformed into a library of 3,6-bis(benzofuran-2-yl)diketopyrrolopyrroles. We show that the presence of a methyl group in a position adjacent to the cyano functionality only slightly decreased the yield of diketopyrrolopyrroles (to 30-57%). An analysis of the relationship between the degree of polarization/planarization of aryl-diketopyrrolopyrroles and their one-and two-photon spectroscopic properties is reported. Careful design of the desired dyes and enhanced control of their ability to assume a planar molecular structure resulted in interesting photophysical properties, such as absorption and emission in the so-called biological window. Despite having less promising linear spectroscopic properties, the deplanarized molecules possess pretty strong two-photon absorbing properties. Placing methyl groups at adjacent positions to the linkage between benzofuran and the DPP core caused the formation of yellow-emitting dyes with almost quantitative fluorescence quantum yield, moderate Stokes shift and reasonable two-photon absorption cross-sections.

OriginalsprogEngelsk
TidsskriftOrganic Chemistry Frontiers
Vol/bind4
Udgave nummer5
Sider (fra-til)724-736
ISSN2052-4129
DOI
StatusUdgivet - 2017

Fingeraftryk

Bearings (structural)
Photons
Optical properties
Coloring Agents
Quantum yield
Molecular structure
Catalysis
Condensation
Fluorescence
Polarization
Molecules
benzofuran

Citer dette

Purc, Anna ; Koszarna, Beata ; Iachina, Irina ; Friese, Daniel H. ; Tasior, Mariusz ; Sobczyk, Krzysztof ; Pȩdziński, Tomasz ; Brewer, Jonathan ; Gryko, Daniel T. / The impact of interplay between electronic and steric effects on the synthesis and the linear and non-linear optical properties of diketopyrrolopyrrole bearing benzofuran moieties. I: Organic Chemistry Frontiers. 2017 ; Bind 4, Nr. 5. s. 724-736.
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title = "The impact of interplay between electronic and steric effects on the synthesis and the linear and non-linear optical properties of diketopyrrolopyrrole bearing benzofuran moieties",
abstract = "An in-depth investigation of the reaction of substituted salicylaldehydes with chloroacetonitrile led to the development of new conditions for the synthesis of 2-cyanobenzofurans. The crucial improvement lies in the use of phase-transfer catalysis in the second step, i.e., intramolecular aldol type condensation. In a two-step process, the reactants were transformed into a library of 3,6-bis(benzofuran-2-yl)diketopyrrolopyrroles. We show that the presence of a methyl group in a position adjacent to the cyano functionality only slightly decreased the yield of diketopyrrolopyrroles (to 30-57{\%}). An analysis of the relationship between the degree of polarization/planarization of aryl-diketopyrrolopyrroles and their one-and two-photon spectroscopic properties is reported. Careful design of the desired dyes and enhanced control of their ability to assume a planar molecular structure resulted in interesting photophysical properties, such as absorption and emission in the so-called biological window. Despite having less promising linear spectroscopic properties, the deplanarized molecules possess pretty strong two-photon absorbing properties. Placing methyl groups at adjacent positions to the linkage between benzofuran and the DPP core caused the formation of yellow-emitting dyes with almost quantitative fluorescence quantum yield, moderate Stokes shift and reasonable two-photon absorption cross-sections.",
author = "Anna Purc and Beata Koszarna and Irina Iachina and Friese, {Daniel H.} and Mariusz Tasior and Krzysztof Sobczyk and Tomasz Pȩdziński and Jonathan Brewer and Gryko, {Daniel T.}",
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doi = "10.1039/c6qo00869k",
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pages = "724--736",
journal = "Organic Chemistry Frontiers",
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The impact of interplay between electronic and steric effects on the synthesis and the linear and non-linear optical properties of diketopyrrolopyrrole bearing benzofuran moieties. / Purc, Anna; Koszarna, Beata; Iachina, Irina; Friese, Daniel H.; Tasior, Mariusz; Sobczyk, Krzysztof; Pȩdziński, Tomasz; Brewer, Jonathan; Gryko, Daniel T.

I: Organic Chemistry Frontiers, Bind 4, Nr. 5, 2017, s. 724-736.

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningpeer review

TY - JOUR

T1 - The impact of interplay between electronic and steric effects on the synthesis and the linear and non-linear optical properties of diketopyrrolopyrrole bearing benzofuran moieties

AU - Purc, Anna

AU - Koszarna, Beata

AU - Iachina, Irina

AU - Friese, Daniel H.

AU - Tasior, Mariusz

AU - Sobczyk, Krzysztof

AU - Pȩdziński, Tomasz

AU - Brewer, Jonathan

AU - Gryko, Daniel T.

PY - 2017

Y1 - 2017

N2 - An in-depth investigation of the reaction of substituted salicylaldehydes with chloroacetonitrile led to the development of new conditions for the synthesis of 2-cyanobenzofurans. The crucial improvement lies in the use of phase-transfer catalysis in the second step, i.e., intramolecular aldol type condensation. In a two-step process, the reactants were transformed into a library of 3,6-bis(benzofuran-2-yl)diketopyrrolopyrroles. We show that the presence of a methyl group in a position adjacent to the cyano functionality only slightly decreased the yield of diketopyrrolopyrroles (to 30-57%). An analysis of the relationship between the degree of polarization/planarization of aryl-diketopyrrolopyrroles and their one-and two-photon spectroscopic properties is reported. Careful design of the desired dyes and enhanced control of their ability to assume a planar molecular structure resulted in interesting photophysical properties, such as absorption and emission in the so-called biological window. Despite having less promising linear spectroscopic properties, the deplanarized molecules possess pretty strong two-photon absorbing properties. Placing methyl groups at adjacent positions to the linkage between benzofuran and the DPP core caused the formation of yellow-emitting dyes with almost quantitative fluorescence quantum yield, moderate Stokes shift and reasonable two-photon absorption cross-sections.

AB - An in-depth investigation of the reaction of substituted salicylaldehydes with chloroacetonitrile led to the development of new conditions for the synthesis of 2-cyanobenzofurans. The crucial improvement lies in the use of phase-transfer catalysis in the second step, i.e., intramolecular aldol type condensation. In a two-step process, the reactants were transformed into a library of 3,6-bis(benzofuran-2-yl)diketopyrrolopyrroles. We show that the presence of a methyl group in a position adjacent to the cyano functionality only slightly decreased the yield of diketopyrrolopyrroles (to 30-57%). An analysis of the relationship between the degree of polarization/planarization of aryl-diketopyrrolopyrroles and their one-and two-photon spectroscopic properties is reported. Careful design of the desired dyes and enhanced control of their ability to assume a planar molecular structure resulted in interesting photophysical properties, such as absorption and emission in the so-called biological window. Despite having less promising linear spectroscopic properties, the deplanarized molecules possess pretty strong two-photon absorbing properties. Placing methyl groups at adjacent positions to the linkage between benzofuran and the DPP core caused the formation of yellow-emitting dyes with almost quantitative fluorescence quantum yield, moderate Stokes shift and reasonable two-photon absorption cross-sections.

U2 - 10.1039/c6qo00869k

DO - 10.1039/c6qo00869k

M3 - Journal article

AN - SCOPUS:85021784921

VL - 4

SP - 724

EP - 736

JO - Organic Chemistry Frontiers

JF - Organic Chemistry Frontiers

SN - 2052-4129

IS - 5

ER -