Synthesis of Emissive Heteroacene Derivatives via Nucleophilic Aromatic Substitution

In this contribution, we report on a class of emitters based on bridged oxo‐ and/or thioethers revealing striking photoluminescence properties in fluid solution and in the solid state. In total, nine compounds were investigated concerning their photophysical properties, which were interpreted by quantum chemical calculations. To our delight, we discovered compounds possessing nearly identical photoluminescence quantum yields (ΦF) in solution and in the solid state, which has been rarely reported so far. Besides these efforts, we shed light on the influence of polymorphism and solvent polarity on the emission properties. In addition, an in‐depth X‐ray diffractometric analysis was conducted to correlate molecular packing in the crystal with differences in the photophysical properties.

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“…[g] Amplitude‐weighted average fluorescence lifetimes in the solid state. [h] Data were partially reported in literature [17,18a] …”

Section: Resultsmentioning

confidence: 99%

Bridged Aromatic Oxo‐ and Thioethers with Intense Emission in Solution and the Solid State

Riebe

Adam

Roy

et al. 2021

Chemistry An Asian Journal

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“…Our previous studies focused on nucleophilic substitution reactions of bidentate nucleophiles with tetrafluoroterephthalonitrile to furnish a series of heteropentacene analogues, where the solid state structures and crystal packing of these compounds were described. , Using this methodology, compounds 1 – 6 were conveniently accessed via nucleophilic aromatic substitution of a fluorinated arene with either catechol or a 2-aminophenol derivative.…”

Section: Resultsmentioning

confidence: 99%

“…Dibenzo- p -dioxins 1 and 3 were synthesized according to literature procedures with minor modifications (see Supporting Information for full synthetic procedures and characterization). , Novel dibenzo- p -dioxin 2 was prepared in like manner via nucleophilic aromatic substitution of the appropriate 2,3,4,5-tetrafluorobenzene and catechol in DMF with excess K 2 CO 3 . Phenoxazines 4 – 6 were obtained similarly by reaction of the appropriate 2-aminophenol nucleophile and tetrafluoroterephthalonitrile . In the case of 10 H -phenoxazine 4 , no base was used.…”

Section: Methodsmentioning

confidence: 99%

“…Phenoxazines 4−6 were obtained similarly by reaction of the appropriate 2-aminophenol nucleophile and tetrafluoroterephthalonitrile. 23 In the case of 10H-phenoxazine 4, no base was used. After isolation and purification (crystallization/column chromatography), single crystals were grown by slow solvent diffusion or evaporation.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

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Crystal Packing of a Series of 1,2,3,4-Substituted Phenoxazine and Dibenzodioxin Heterocycles

Hiscock

Malý

2019

Crystal Growth & Design

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Understanding and control of weak intermolecular interactions, including π-interactions, is an element toward the strategic design of supramolecular materials. In this work, we describe an approach to promoting cofacial π-stacking in the solid state by preparing polycyclic aromatic compounds that bear complementary electron-rich and electron-poor rings. Specifically, we describe the synthesis and single crystal structures of a series of six dissymmetric systems (three dibenzo-p-dioxins and three phenoxazines) comprised of one electron-rich and one electron-deficient ring. In all cases, anti-co-facial π–π interactions were observed, but no significant C–H···π interactions. These observations were compared with similar structures in the Cambridge Structural Database, and it was found that the presence of bulky substituents, lattice solvent, and stronger intermolecular interactions interfere with efficient π-stacking. Both qualitative and quantitative evaluations of the newly reported structures, and database examples, are included.

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“…Hiscock et al. studied the influence of main group change, instituting nitrogen as the bridging atom with several sulfur and oxygen variations [83] . Unfortunately, only a few compounds were selected for photophysical analysis.…”

Section: The Non‐classic Approach To Sssesmentioning

confidence: 99%

Design Concepts for Solution and Solid‐State Emitters – A Modern Viewpoint on Classical and Non‐Classical Approaches

Huber

Dubbert

Scherz

et al. 2022

Chemistry A European J

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For a long time, luminescence phenomena were strictly distinguished between the emission of isolated molecules in dilute solutions or close‐packed structures such as in powders or aggregates. This changed with the breakthrough observation of dual‐state efficient materials, which led to a rapid boost of publications examining the influence of structural features to achieve balanced emission with disregarded molecular surroundings. Some first general structural design concepts have already been proposed based on reoccurring patterns and pivotal motifs. However, we have found another way to classify these solution and solid‐state emitters (SSSEs). Hence, this minireview aims to present an overview of published structural features of SSSEs while shining light on design concepts from a more generalized perspective. Since SSSEs are believed to bridge the gap of hitherto known aggregation‐sensitive compound classes, we hope to give future scientists a versatile tool in hand to efficiently design novel luminescent materials.

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Synthesis of Emissive Heteroacene Derivatives via Nucleophilic Aromatic Substitution

Cited by 11 publications

References 34 publications

Bridged Aromatic Oxo‐ and Thioethers with Intense Emission in Solution and the Solid State

Bridged Aromatic Oxo‐ and Thioethers with Intense Emission in Solution and the Solid State

Crystal Packing of a Series of 1,2,3,4-Substituted Phenoxazine and Dibenzodioxin Heterocycles

Design Concepts for Solution and Solid‐State Emitters – A Modern Viewpoint on Classical and Non‐Classical Approaches

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