Water‐Soluble Pyrrolo[3,2‐<i>b</i>]pyrroles: Synthesis, Luminescence and Two‐Photon Cellular Imaging Properties

Santra, Mithun; Jun, Yong Woong; Bae, Juryang; Sarkar, Sourav; Choi, Wonchang; Gryko, Daniel T.; Ahn, Kyo Han

doi:10.1002/ajoc.201600613

Cited by 16 publications

(10 citation statements)

References 19 publications

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“…31 The same pyridinyl derivative has been utilized in the synthesis of 61, the first water-soluble analogue comprising the pyrrolo[3,2-b]pyrrole core (Scheme 5). 32 ■ π-EXPANSION OF TAPPS Linking a given chromophore with another aromatic unit via a carbon−carbon triple bond is the most popular strategy for synthesizing organic π-conjugated materials. As pointed out earlier, 3,6-dibromo-TAPPs do not undergo Sonogashira reaction.…”

Section: ■ Reactivity Of Tappsmentioning

confidence: 99%

The Tetraarylpyrrolo[3,2-b]pyrroles—From Serendipitous Discovery to Promising Heterocyclic Optoelectronic Materials

2017

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Progress in organic optoelectronics requires compounds possessing a suitable combination of photophysical and electronic properties. Another key constraint encompasses the availability of feasible, and hopefully scalable, synthetic procedures for preparing the molecular scaffolds of interest. A multicomponent reaction of aromatic aldehydes, aromatic amines, and butane-2,3-dione that was discovered in 2013 gives straightforward access to previously unavailable 1,2,4,5-tetraarylpyrrolo[3,2-b]pyrroles. These dyes are examples of heteropentalenes-a class of 10-π-electron aromatic compounds. The unsurpassed variety of aromatic aldehydes and primary aromatic amines, which are commercially available or easy to prepare, allows for potential routes to thousands of 1,2,4,5-tetraarylpyrrolo[3,2-b]pyrroles that are currently unknown. This synthetic procedure offers a means for preparing the pyrrolopyroles in gram quantities and isolating them by simple filtration. Typically, the construction of an aromatic core is merely the first phase in a long procedure toward multistep functionalization. Conversely, the synthesis of 1,2,4,5-tetraarylpyrrolo[3,2-b]pyrroles leads to preinstalled substituents in frames with C symmetry, which "opens Sesame" to a wealth of structural possibilities. In addition, steric hindrance of the aldehyde components, rather than presenting a problem, is beneficial for increasing the yields of the products. This feature provides invaluable routes for the synthesis of a broad range of π-extended systems possessing the pyrrolo[3,2-b]pyrrole core in just a few steps. Indeed, this approach has enabled the preparation of a large number of previously unknown ladder-type heteroacenes possessing additional rings based on carbon-carbon, carbon-nitrogen, and nitrogen-nitrogen double bonds as well as nitrogen-boron single bonds. This set of chromophores includes planar and curved structures bearing up to 14 conjugated rings. 1,2,4,5-Tetraarylpyrrolo[3,2-b]pyrroles manifest broad absorption bands between about 300 and 450 nm, strong violet-blue or blue fluorescence with typical quantum yields of ∼60%, significant Stokes shifts ranging between 3000 and 5800 cm, and emission while in the solid state. Should the two peripheral aryl groups have an electron-deficient character, the two-photon absorption cross section also becomes pronounced, i.e., ∼400 GM. Perhaps the most important feature of these dyes is their strong solvatofluorochromism, which predestines their value as environment-sensitive probes. Extension of the π-conjugation of 1,2,4,5-tetraarylpyrrolo[3,2-b]pyrroles enables further modifications of their photophysical properties, such as shifting the emission bathochromically, increasing the Stokes shift beyond 10 000 cm, and attaining solvatofluorochromism for curved, butterfly-shaped analogues without a decrease in emission intensity when the solvent polarity is increased. Common features of these chromophores include a significant difference between the geometries of their relaxed ground and relaxed excited ...

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Section: ■ Reactivity Of Tappsmentioning

confidence: 99%

The Tetraarylpyrrolo[3,2-b]pyrroles—From Serendipitous Discovery to Promising Heterocyclic Optoelectronic Materials

2017

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“…A relatively under-explored class of hetero pentalenes such as 1,4-dihydropyrrolo[3,2– b ]pyrroles (DHPPs) is known to exhibit interesting optical and electrical properties. , Their potential applications in cellular-imaging, nonlinear optics, , and halocarbon sensing are known to date. Recently, our group reported the amphoteric redox behavior of DHPPs and their applications in organic memory devices for the first time .…”

Section: Introductionmentioning

confidence: 99%

1,4-Dihydropyrrolo[3,2-b]pyrroles as a Single Component Photoactive Layer: A New Paradigm for Broadband Detection

Balasubramanyam

Kandjani

Harrison

et al. 2017

ACS Appl. Mater. Interfaces

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Single component organic photodetectors capable of broadband light sensing represent a paradigm shift for designing flexible and inexpensive optoelectronic devices. The present study demonstrates the application of a new quadrupolar 1,4-dihydropyrrolo[3,2-b]pyrrole derivative with spectral sensitivity across 350-830 nm as a potential broadband organic photodetector (OPD) material. The amphoteric redox characteristics evinced from the electrochemical studies are exploited to conceptualize a single component OPD with ITO and Al as active electrodes. The photodiode showed impressive broadband photoresponse to monochromatic light sources of 365, 470, 525, 589, 623, and 830 nm. Current density-voltage (J-V) and transient photoresponse studies showed stable and reproducible performance under continuous on/off modulations. The devices operating in reverse bias at 6 V displayed broad spectral responsivity (R) and very good detectivity (D*) peaking a maximum 0.9 mA W and 1.9 × 10 Jones (at 623 nm and 500 μW cm) with a fast rise and decay times of 75 and 140 ms, respectively. Low dark current densities ranging from 1.8 × 10 Acm at 1 V to 7.2 × 10 A cm at 6 V renders an operating range to amplify the photocurrent signal, spectral responsivity, and detectivity. Interestingly, the fabricated OPDs display a self-operational mode which is rarely reported for single component organic systems.

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“…Materials and chemicals : 1 was obtained according to a previously reported method [12] . Salicylic acid ( a ) and dibromomethane were purchased from Tokyo Chemical Industry Co., Ltd. (Japan).…”

Section: Methodsmentioning

confidence: 99%

Insights into Proton Dynamics in a Photofunctional Salt‐Cocrystal Continuum: Single‐Crystal X‐ray, Neutron Diffraction, and Hirshfeld Atom Refinement

Yano

Ono

Ohhara

et al. 2021

Chemistry A European J

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X‐ray diffraction, neutron diffraction, and theoretical calculations were used to investigate the relationship between the optical properties and degree of protonation in acid‐base complexes. We prepared five acid‐base complexes by using a pyridine‐modified pyrrolopyrrole derivative and salicylic acid. Two of the prepared acid‐base complexes were polymorphs of guest‐free crystals with green emission; the other three were guest‐inclusion crystals with yellow emission containing CH2Cl2, CH2Br2, or C2H4Cl2. The presence or absence of guests caused the emission to change color, altering the hydrogen bond strength between the acid‐base complexes. Accurate N⋅⋅⋅H distances between the pyridyl moiety and the carboxy group over the temperature range 123 to 273 K were 1.40 Å for the guest‐free crystals and 1.25 Å for the guest‐inclusion crystals. Our findings contribute to a better understanding of the complex relationship between photofunction and proton dynamics in acid‐base complexes.

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Water‐Soluble Pyrrolo[3,2‐b]pyrroles: Synthesis, Luminescence and Two‐Photon Cellular Imaging Properties

Cited by 16 publications

References 19 publications

The Tetraarylpyrrolo[3,2-b]pyrroles—From Serendipitous Discovery to Promising Heterocyclic Optoelectronic Materials

The Tetraarylpyrrolo[3,2-b]pyrroles—From Serendipitous Discovery to Promising Heterocyclic Optoelectronic Materials

1,4-Dihydropyrrolo[3,2-b]pyrroles as a Single Component Photoactive Layer: A New Paradigm for Broadband Detection

Insights into Proton Dynamics in a Photofunctional Salt‐Cocrystal Continuum: Single‐Crystal X‐ray, Neutron Diffraction, and Hirshfeld Atom Refinement

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