Ruthenium‐Catalyzed Oxidation of the Porphyrin β,β′‐Pyrrolic Ring: A General and Efficient Approach to Porpholactones

Yu, Yi; Lv, Hongbin; Ke, Xian‐Sheng; Yang, Boyan; Zhang, Junlong

doi:10.1002/adsc.201200720

Cited by 53 publications

(60 citation statements)

References 30 publications

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“…Their better solubility renders the fluorinated derivatives to be a great platform for many modification reactions, including their one-step conversion to the corresponding (metallo)porpholactones T F PL/T F PLM. We found the RuCl 3 /Oxone ® -mediated oxidation pathway, as described by Zhang and co-workers [ 41 ], to be the most efficient pathway to generate free base T F PL as well as T F PLMs (for M = Zn II or Pt II ) by oxidation of the corresponding porphyrin metal complexes T F PPM (for M = Zn II or Pt II ). The reaction was described to be more suitable for substrates bearing electron-withdrawing meso -substituents [ 41 ].…”

Section: Resultsmentioning

confidence: 60%

“…In this contribution, we like to delineate in detail the most efficient paths toward TPL/TPLZn/TPLPt and T F PL/T F PLZn/T F PLPt we are aware of, with the aim of providing the non-specialist access to these intriguing and versatile materials. The procedures spelled out (see Supporting Information ) were derived from published methods developed by us [ 4 ], or the research group of Zhang [ 41 ], and tested multiple times in our laboratories. The detailed procedures incorporate hitherto unpublished practical details.…”

Section: Introductionmentioning

confidence: 99%

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Oxazolochlorins 21. Most Efficient Access to meso-Tetraphenyl- and meso-Tetrakis(pentafluorophenyl)porpholactones, and Their Zinc(II) and Platinum(II) Complexes

2020

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meso-Phenyl- and meso-pentafluorophenyl-porpholactones, their metal complexes, as well as porphyrinoids directly derived from them are useful in a number of technical and biomedical applications, and more uses are expected to be discovered. About a dozen competing and complementary pathways toward their synthesis were reported. The suitability of the methods changes with the meso-aryl group and whether the free base or metal derivatives are sought. These circumstances make it hard for anyone outside of the field of synthetic porphyrin chemistry to ascertain which pathway is the best to produce which specific derivative. We report here on what we experimentally evaluated to be the most efficient pathways to generate the six key compounds from the commercially available porphyrins, meso-tetraphenylporphyrin (TPP) and meso-tetrakis(pentafluorophenyl)porphyrin (TFPP): free base meso-tetraphenylporpholactone (TPL) and meso-tetrakis(pentafluorophenyl)porpholactone (TFPL), and their platinum(II) and zinc(II) complexes TPLPt, TFPLPt, TPLZn, and TFPLZn, respectively. Detailed procedures are provided to make these intriguing molecules more readily available for their further study.

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Section: Resultsmentioning

confidence: 60%

Section: Introductionmentioning

confidence: 99%

Oxazolochlorins 21. Most Efficient Access to meso-Tetraphenyl- and meso-Tetrakis(pentafluorophenyl)porpholactones, and Their Zinc(II) and Platinum(II) Complexes

2020

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“…Synthesis of Yb‐1 a : Porpholactones were prepared according to our modified procedure 5f . Yb‐1 a was prepared according to a procedure similar to that described in the literature 3a.…”

Section: Methodsmentioning

confidence: 99%

Ytterbium(III) Porpholactones: β‐Lactonization of Porphyrin Ligands Enhances Sensitization Efficiency of Lanthanide Near‐Infrared Luminescence

Yang

Cheng

et al. 2014

Chemistry A European J

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The near-infrared (NIR) luminescence efficiency of lanthanide complexes is largely dependent on the electronic and photophysical properties of antenna ligands. Although porphyrin ligands are efficient sensitizers of lanthanide NIR luminescence, non-pyrrolic porphyrin analogues, which have unusual symmetry and electronic states, have been much less studied. In this work, we used porpholactones, a class of β-pyrrolic-modified porphyrins, as ligands and investigated the photophysical properties of lanthanide porpholactones Yb-1 a-5 a. Compared with Yb porphyrin complexes, the porpholactone complexes displayed remarkable enhancement of NIR emission (50-120 %). Estimating the triplet-state levels of porphyrin and porpholactone in Gd complexes revealed that β-lactonization of porphyrinic ligands lowers the ligand T1 state and results in a narrow energy gap between this state and the lowest excited state of Yb(3+) . Transient absorption spectra showed that Yb(III) porpholactone has a longer transient decay lifetime at the Soret band than the porphyrin analogue (30.8 versus 17.0 μs). Thus, the narrower energy gap and longer lifetime arising from β-lactonization are assumed to enhance NIR emission of Yb porpholactones. To demonstrate the potential applications of Yb porpholactone, a water-soluble Yb bioprobe was constructed by conjugating glucose to Yb-1 a. Interestingly, the NIR emission of this Yb porpholactone could be specifically switched on in the presence of glucose oxidase and then switched off by addition of glucose. This is the first demonstration that non-pyrrolic porphyrin ligands enhance the sensitization efficiency of lanthanide luminescence and also display switchable NIR emission in the region of biological analytes (800-1400 nm).

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“…Known Porphyrinoid ([meso-tetrakis(pentafluorophenyl)porpholactonato]Platinum(II), T F PLPt; MW = 1195 g/mol) was prepared as described previously along the [mesotetrakis(pentafluorophenyl)porphyrin dihydroxylation, oxidation, and platinum insertion pathway [23,27], but alternative pathways toward this molecule are also available [28,29] [30]. We adjusted the pH levels ranging from pH 13.5 down to pH 8.0 using aqueous HCl.…”

Section: Sensor Compoundmentioning

confidence: 99%

Mapping high pH levels in hydrated calcium silicates

Liu

Ghandehari

Brückner

et al. 2017

Cement and Concrete Research

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Data on the variability of pH levels in cement-based materials is essential for a better understanding of the early aging of materials and the long-term performance of concrete structures. Current approaches for measuring pH levels in concrete are inadequate with respect to radiometric range and resolution and spatial granularity. We report on a methodology for mapping pH levels in concrete utilizing a halochromic porphyrin sensor molecule that allows a simple measurement of surface values of pH level using a commercial digital camera setup. As proof of concept, cement paste, mortar, and concrete samples were subject to accelerated carbonation and then evaluated for pH profiles at different ages of degradation. Comparative tests on the same specimens were also conducted using phenolphthalein as the pH indicator. Spatial distribution of pH level from pH 11.0 to 13.5 were mapped at various levels of carbonation.

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Ruthenium‐Catalyzed Oxidation of the Porphyrin β,β′‐Pyrrolic Ring: A General and Efficient Approach to Porpholactones

Cited by 53 publications

References 30 publications

Oxazolochlorins 21. Most Efficient Access to meso-Tetraphenyl- and meso-Tetrakis(pentafluorophenyl)porpholactones, and Their Zinc(II) and Platinum(II) Complexes

Oxazolochlorins 21. Most Efficient Access to meso-Tetraphenyl- and meso-Tetrakis(pentafluorophenyl)porpholactones, and Their Zinc(II) and Platinum(II) Complexes

Ytterbium(III) Porpholactones: β‐Lactonization of Porphyrin Ligands Enhances Sensitization Efficiency of Lanthanide Near‐Infrared Luminescence

Mapping high pH levels in hydrated calcium silicates

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