Bis[1]benzothieno[1,4]thiazines: Planarity, Enhanced Redox Activity and Luminescence by Thieno‐Expansion of Phenothiazine

Schneeweis, Arno P. W.; Hauer, Simone T.; Reiß, Guido J.; Müller, Thomas J. J.

doi:10.1002/chem.201805085

Cited by 14 publications

(36 citation statements)

References 98 publications

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“…In previous studies, we could show that photophysical and electrochemical properties of syn-syn dithieno[1,4]thiazines 2a can be fine-tuned by substitution [11] or by benzoanellation. [12] Constitutional modification of the established syn-syn dithieno[1,4]thiazine system 2a can prove to be favorable for the tuning of electronic properties and setting the stage for new applications. Herein, we communicatef irst syntheses, ground and excited state electronic properties and electronic structures of three novel dithieno[1,4]thiazine constitutionalisomers (syn-exo 2b, exo-exo 2c and anti-anti 2d,a ll with R = Ph) in comparison to the syn-syn dithieno[1,4]thiazine isomer 2a (R = Ph) and the analoguep henothiazine 1 (R = Ph).…”

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confidence: 99%

Electron‐Rich Phenothiazine Congeners and Beyond: Synthesis and Electronic Properties of Isomeric Dithieno[1,4]thiazines

May

Müller

2020

Chemistry A European J

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A series of isomeric dithieno[1,4]thiazines is accessible through an intermolecular–intramolecular Buchwald–Hartwig amination starting from dihalodithienyl sulfides. The electronic properties of dithieno[1,4]thiazine isomers differ conspicuously over a broad range depending on the thiophene–thiazine anellation: a large cathodic (340 mV) or an anodic shift (130 mV) of the redox potentials relative to corresponding phenothiazines is possible. Structure–property relationships of the dithieno[1,4]thiazine constitution derived from DFT calculations and cyclic voltammetry not only reveal increased electron density but also different delocalization of the radical cations that determines the electrochemical properties significantly. In addition, photophysical properties (absorption and emission) qualify dithieno[1,4]thiazines as promising substitutes of phenothiazine and beyond due to increased tunable electron richness.

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confidence: 99%

Electron‐Rich Phenothiazine Congeners and Beyond: Synthesis and Electronic Properties of Isomeric Dithieno[1,4]thiazines

May

Müller

2020

Chemistry A European J

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“…There are three regioisomers, the syn-syn, the syn-anti and the anti-anti isomer (Scheme 16). Their synthesis is generally in accordance with the synthesis of the dithieno [1,4]thiazines 2 (Scheme 4) [49,50]. A broad spectrum of N-functionalization, including electron-withdrawing and electron-donating N-aryl substituents, is also accessible.…”

Section: Expansion Of the π-System By Anellation: Bis[1]benzothieno[1mentioning

confidence: 93%

“…Scheme 16. Synthesized bis [1]benzothieno [1,4]thiazine regioisomers 9 ( a Additional examples of 9b were obtained as side products in the synthesis of syn-syn isomers 9a) [49,50].…”

Section: Expansion Of the π-System By Anellation: Bis[1]benzothieno[1mentioning

confidence: 99%

“…The benzo-anellated 2,2 -and 3,3 -dithienyl sulfides 10 have been similarly synthesized to the dithienyl sulfides by introducing the sulfide bridge using bis(phenylsulfonyl)sulfide 4 (Scheme 5). However, the 2,3-dithienyl sulfide 10c has been prepared via an Ullmann-type CS-coupling (Scheme 17) [50].…”

Section: Expansion Of the π-System By Anellation: Bis[1]benzothieno[1mentioning

confidence: 99%

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Dithieno[1,4]thiazines and Bis[1]benzothieno[1,4]thiazines—Organometallic Synthesis and Functionalization of Electron Density Enriched Congeners of Phenothiazine

May

Müller

2020

Molecules

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This mini-review summarizes the syntheses and functionalizations of dithieno[1,4]thiazines and bis[1]benzothieno[1,4]thiazines, both electron density-enriched congeners of phenothiazines with remarkable electronic properties. Diversity-oriented, straightforward, and efficient syntheses, including versatile one-pot processes, have been developed for the anellated 1,4-thiazines as well as various functionalization for the expansion of the π-systems. Thereby, syntheses of different regioisomers depending on the (benzo)thieno-thiazine anellation are discussed, which exert a deep impact on the electronic properties. The tunable photophysical and electrochemical properties of dithieno[1,4]thiazines and bis[1]benzothieno[1,4]thiazines outscore phenothiazines on many points and promise an enormous potential in molecular electronics and applications beyond.

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“…的近红外荧光染料可以分为以下几类: 菁染料 [12][13][14][15] 、含四吡咯基团的近红外荧光染料 [16] 、咕吨类荧光染料 [17] 、噻嗪类和嗯嗪类近红外荧光染料 [18] 、二氟化硼-二吡咯甲烷荧光染料 [19][20][21][22] 等.…”

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Synthesis and Optical Properties of Different Substituted-Indole-Modified Squaraine Derivatives

Zhang¹,

Yuan²,

Xu³

et al. 2020

Chin. J. Org. Chem.

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Four squaraine derivatives SQ, DISQ, MeSQ and DIMeSQ with different substitution indole modifications were synthesized through condensation reaction. Squaraine derivative is one kind of D-AD configuration dyes, which is formed by connecting squaraine with two electron-rich groups through conjugation. The squaraine derivatives were characterized by 1 H NMR, 13 C NMR and high resolution mass spectrometry. The photophysical properties of these squaraine derivatives were studied, such as UV-visible absorption, fluorescence emission, fluorescence quantum yield, fluorescence lifetimes, singlet oxygen quantum yields, and so on. The results showed that, SQ, DISQ, MeSQ and DIMeSQ showed stronger absorption band at 600～700 nm and emission band at 620～800 nm in dichloromethane, which were in near-infrared filed. These four squaraine derivatives were used for singlet oxygen generation, and the highest singlet oxygen quantum yield (6%) was observed for DISQ, which is twice as high as that of DIMeSQ (3%). It is proposed that iodine-substituted and N-hydrogensubstituted molecules are more conducive to intersystem crossing than N-methyl substituted molecules. In addition, It is confirmed that the intramolecular N-H…O force is beneficial to the intersystem crossing of molecules by combining single crystal structure and theoretical calculations. It showed that DISQ could be used as a potential drug for photodynamic therapy.

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Bis[1]benzothieno[1,4]thiazines: Planarity, Enhanced Redox Activity and Luminescence by Thieno‐Expansion of Phenothiazine

Cited by 14 publications

References 98 publications

Electron‐Rich Phenothiazine Congeners and Beyond: Synthesis and Electronic Properties of Isomeric Dithieno[1,4]thiazines

Electron‐Rich Phenothiazine Congeners and Beyond: Synthesis and Electronic Properties of Isomeric Dithieno[1,4]thiazines

Dithieno[1,4]thiazines and Bis[1]benzothieno[1,4]thiazines—Organometallic Synthesis and Functionalization of Electron Density Enriched Congeners of Phenothiazine

Synthesis and Optical Properties of Different Substituted-Indole-Modified Squaraine Derivatives

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