Synthesis of meso‐Substituted Tetrabenzotriazaporphyrins: Easy Access to Hybrid Macrocycles

Díaz‐Moscoso, Alejandro; Tizzard, Graham J.; Coles, Simon J.; Cammidge, Andrew N.

doi:10.1002/ange.201306151

Cited by 7 publications

(7 citation statements)

References 13 publications

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“…With sufficient quantities of compounds 3a–c in hand, we decided to test their potential use as precursors for the preparation of more complex chromophores, as has been demonstrated for a number of DII derivatives, , as well as on new hybrid isoindol-1-imines (Scheme ). − Initially, the potential for self-condensation reactions of heterocycles 3a–c , which would give us a new class of benzo-fused core-extended azadipyrromethene analogs, was studied in detail. We found that under refluxing conditions for a prolonged time in non-polar solvents such as toluene or o -xylene, the formation of new products can be observed by the color change of the reaction mixture.…”

Section: Resultsmentioning

confidence: 99%

“…42 At the same time, a very limited number of synthetic strategies have been proposed for the synthesis of isoindol-1imine derivatives, 43,44 with, to the best of our knowledge, only one method reported for the preparation of 3-alkylideneisoindol-1-imine: 45 the microwave-assisted, palladium-catalyzed reaction of 2-bromobenzamide with phenylacetylene. Cammidge and co-workers recently described the synthesis of new hybrid meso-substituted tetrabenzotriazaporphyrins, 46 new hybrid boron subphthalocyanine−subporphyrin systems, 47 as well as aza-BODIPY type compounds 48 starting from such isoindol-1-imines (Chart 1).…”

Section: ■ Introductionmentioning

confidence: 99%

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Development of a Class of Easily Scalable, Electron-Deficient, Core-Extended Benzo-Fused Azadipyrromethene Derivatives (“MB-DIPY”)

et al. 2019

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We have developed a new synthetic strategy for the preparation of a series of isoindolin-1-imines and isoindolin-1-ones from aromatic ketones and phthalonitrile. Self-condensation reactions of these isoindolin-1-imines led to the formation of a novel class of benzo-fused, highly electron-deficient core-extended azadipyrromethene chromophores ("MB-DIPY"). The influence of temperature, catalyst, and the template ions on the self-condensation reaction rate, yield, and stereoselectivity was examined in detail. New chromophores (sodium, zinc, and metal-free compounds) were characterized by NMR, UV−vis, fluorescence, high-resolution mass spectroscopies, and in many cases, Xray crystallography. Their redox properties were probed by electrochemical and spectroelectrochemical approaches that revealed the remarkable electron-accepting nature of the new systems. Stepwise one-and two-electron reduction of the new MB-DIPYs and their zinc complexes was investigated by spectroscopic and spectroelectrochemical methods. Both one-and two-electron reduced forms of all zinc complexes studied have strong absorption in the near-infrared region up to ∼1200 nm. Unusual spectroscopic and electrochemical properties of these dyes were correlated with their electronic structures and excitedstate natures predicted by density functional theory (DFT) and time-dependent DFT calculations. Despite some structural similarities with well-known aza-BODIPYs, the new MB-DIPYs differ remarkably from them in spectroscopic and redox properties.

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Section: Resultsmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Development of a Class of Easily Scalable, Electron-Deficient, Core-Extended Benzo-Fused Azadipyrromethene Derivatives (“MB-DIPY”)

et al. 2019

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“…Our synthesis of meso ‐aryl tetrabenzotriazaporphyrins (TBTAPs) provided, for the first time, scalable access to these hybrid structures functionalized at the meso position [8] . Based on the proposed mechanism, we recognized that our synthetic protocol had the potential to introduce different benzo fragments ( A and B ) around the macrocycle in a regiospecific manner, in addition to the meso functionality (Scheme 1).…”

Section: Figurementioning

confidence: 99%

“…Access to the full range of (separable and processable) hybrids has further revealed their enhanced behavior as device components [6] . More innovative synthetic inventions have recently started to redefine the field, charting the first steps towards controlled synthesis of di‐ [7] and triaza [8] hybrids.…”

Section: Figurementioning

confidence: 99%

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Complementary Syntheses Giving Access to a Full Suite of Differentially Substituted Phthalocyanine‐Porphyrin Hybrids

et al. 2021

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Phthalocyanines and porphyrins are often the scaffolds of choice for use in widespread applications. Synthetic advances allow bespoke derivatives to be made, tailoring their properties. The selective synthesis of unsymmetrical systems, particularly phthalocyanines, has remained a significant unmet challenge. Porphyrin‐phthalocyanine hybrids offer the potential to combine the favorable features of both parent structures, but again synthetic strategies are poorly developed. Here we demonstrate strategies that give straightforward, controlled access to differentially substituted meso‐aryl‐tetrabenzotriazaporphyrins by reaction between an aryl‐aminoisoindolene (A) initiator and a complementary phthalonitrile (B). The choice of precursors and reaction conditions allows selective preparation of 1:3 Ar‐ABBB and, uniquely, 2:2 Ar‐ABBA functionalized hybrids.

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Synthesis of Meso‐Substituted Subphthalocyanine–Subporphyrin Hybrids: Boron Subtribenzodiazaporphyrins

et al. 2015

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The first syntheses of hybrid structures that lie between subphthalocyanines and subporphyrins are reported. The versatile single‐step synthetic method uses a preformed aminoisoindolene to provide the bridging methine unit and its substituent while trialkoxyborates simultaneously act as Lewis acid, template, and provider of the apical substituent. The selection of each component therefore allows for the controlled formation of diverse, differentially functionalized systems. The new hybrids are isolated as robust, pure materials that display intense absorption and emission in the mid‐visible region. The new compounds are further characterized in solution and solid state by variable‐temperature NMR spectroscopy and X‐ray crystallography, respectively.

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Synthesis of meso‐Substituted Tetrabenzotriazaporphyrins: Easy Access to Hybrid Macrocycles

Cited by 7 publications

References 13 publications

Development of a Class of Easily Scalable, Electron-Deficient, Core-Extended Benzo-Fused Azadipyrromethene Derivatives (“MB-DIPY”)

Development of a Class of Easily Scalable, Electron-Deficient, Core-Extended Benzo-Fused Azadipyrromethene Derivatives (“MB-DIPY”)

Complementary Syntheses Giving Access to a Full Suite of Differentially Substituted Phthalocyanine‐Porphyrin Hybrids

Synthesis of Meso‐Substituted Subphthalocyanine–Subporphyrin Hybrids: Boron Subtribenzodiazaporphyrins

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