meso-Tetraarylporpholactones as high pH sensors

Khalil, Gamal; Daddario, Pedro; Lau, Kimberly S. F.; Imtiaz, Sayed; King, Michelle Annette; Gouterman, Martin; Sidelev, Alexey; Puran, Narissa; Ghandehari, Masoud; Brückner, Christian

doi:10.1039/c0an00018c

Cited by 69 publications

(91 citation statements)

References 46 publications

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“…[21] Many meso-(C 6 F 5 )-substituted porphyrinoids are literature-known, [21][22][23][24] including M A N U S C R I P T A C C E P T E D ACCEPTED MANUSCRIPT 4 N-fused and confused porphyrin 3 and the porpholactone-based halochromic sensor for high pH values 4, [17] other chemosensors and chemophototherapeutics, [25][26][27][28][29][30][31] and detailed studies of their electron injection dynamics into semiconductor surfaces have become known. [32] The (C 6 F 5 )-groups impart excellent solubility to the porphyrinoids and are believed to also protect the chromophores from oxidative degradation.…”

Section: Accepted Manuscriptmentioning

confidence: 99%

Introduction of carboxylic ester and acid functionalities to meso-tetrakis(pentafluorophenyl)porphyrin and their limited electronic effects on the chromophore

et al. 2015

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Please cite this article as: Hewage N, Yang B, Agrios AG, Brückner C, Introduction of Carboxylic Ester and Acid Functionalities to meso-Tetrakis(pentafluorophenyl)porphyrin and their Limited Electronic Effects on the Chromophore, Dyes and Pigments (2015), AbstractAlkyl-or aryl-carboxylic acid-functionalized porphyrinic dyes are sought after because of their propensity to adhere strongly to many metal oxide surfaces as required for their application as, for instance, sensitizers in dye-sensitized solar cells (DSSCs), in air purification, or chemosensing systems. The S N Ar reaction of the pentafluorophenyl group is a versatile method to introduce functionality into meso-pentafluorophenyl-substituted porphyrins. The conditions to introduce one through four alkyl-or aryl-carboxyl functionalities using mercaptopropionate or 3,4-dihydroxybenzoate esters, respectively, are explored, and the regioisomeric products are spectroscopically characterized. Their saponification to the corresponding carboxylic acids was studied. By experimental determination of their optical properties (absorption and emission spectroscopy) and their frontier orbital positions by cyclic voltammetry, we demonstrate the minimal electronic influence this derivatization method has on the chromophore.

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Section: Accepted Manuscriptmentioning

confidence: 99%

Introduction of carboxylic ester and acid functionalities to meso-tetrakis(pentafluorophenyl)porphyrin and their limited electronic effects on the chromophore

et al. 2015

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“…13 This complex can also be utilized as a high pH sensor in the range of pH 11.5–13. 14 Despite their increasing utility and the emergence of their unique reactivity, no full account on the rational, general, and high-yielding synthesis of meso -tetraarylporpholactones has been published to date. In the first part of this report, we will fill this gap by following on our communication.…”

Section: Introductionmentioning

confidence: 99%

“…14,16-19,20 This reaction was adopted by other groups, providing a range of dihydroxychlorins. 10,11,21-23 We further demonstrated the versatility of the chlorin diols as starting material for the preparation of porphyrinoids containing non-pyrrolic building blocks using our versatile ‘breaking and mending’ strategy.…”

Section: Introductionmentioning

confidence: 99%

meso-Arylporpholactones and their Reduction Products

et al. 2012

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The rational syntheses of meso-tetraaryl-3-oxo-2-oxaporphyrins 5, known as porpholactones, via MnO 4 − mediated oxidations of the corresponding meso-tetraaryl-2,3dihydroxychlorins ( 7) is detailed. Since chlorin 7 is prepared from the parent porphyrin 1, this amounts to a 2-step replacement of a pyrrole moiety in 1 by an oxazolone moiety. The stepwise reduction of the porpholactone 5 results in the formation of chlorin analogues, meso-tetraaryl-3-hydroxy-2oxachlorin ( 11) and meso-tetraaryl-2-oxachlorins (12). The reactivity of 11 with respect to nucleophilic substitution by O-, N-, and S-nucleophiles is described. The profound photophysical consequences of the formal replacement of a pyrrole with an oxazolone (porphyrin-like chromophore) or (substituted) oxazole moiety (chlorin-like chromophore with, for the parent oxazolochlorin 12, red-shifted Q x band with enhanced oscillator strengths) are detailed and rationalized on the basis of SAC−CI and MNDO-PSDCI molecular orbital theory calculations. The single crystal X-ray structures of the porpholactones point at a minor steric interaction between the carbonyl oxygen and the flanking phenyl group. The essentially planar structures of all chromophores in all oxidation states prove that the observed optical properties originate from the intrinsic electronic properties of the chromophores and are not subject to conformational modulation.

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“…5 Is the free base high-pH sensor 6 F -PEG 1000 also suitable as low-pH sensor? The question can, in principle, be answered in the affirmative.…”

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confidence: 99%

High pH sensing with water-soluble porpholactone derivatives and their incorporation into a Nafion® optode membrane

Worlinsky

Halepas

Ghandehari

et al. 2015

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The known optical high pH sensing chromophores, free base and metal complexes (M = 2H, Zn(ii), Pt(ii)) of meso-tetrakis(pentafluorophenyl)porpholactone, and the as yet untested Ga(iii) complex, were made freely water-soluble by derivatization at the aryl group with PEG chains. Their halochromic response profiles were determined and found to be surprisingly shifted toward greater base sensitivity when compared to the parent sensors in aqueous solution in the presence of a surfactant. Select PEG-derivatized chromophores were also incorporated into Nafion®-based membranes. The immobilized sensor was shown to be suitable for a moderately rapid (response time in minutes) sensing of high concentrations of hydroxides (pH 11 and above, up to 5 M NaOH concentrations). The lesser sensitivity of the indicators in the membrane is rationalized by the anionic nature of the membrane material. The membrane shows a perfectly reversible response and remains transparent and stable even under extended times of exposure to very caustic environments, and no leaching of the chromophore is observed. The membrane might find use in fiber optics-based optodes suitable for the monitoring of high hydroxide environments inside chemical reactors or fuel cells.

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meso-Tetraarylporpholactones as high pH sensors

Cited by 69 publications

References 46 publications

Introduction of carboxylic ester and acid functionalities to meso-tetrakis(pentafluorophenyl)porphyrin and their limited electronic effects on the chromophore

Introduction of carboxylic ester and acid functionalities to meso-tetrakis(pentafluorophenyl)porphyrin and their limited electronic effects on the chromophore

meso-Arylporpholactones and their Reduction Products

High pH sensing with water-soluble porpholactone derivatives and their incorporation into a Nafion® optode membrane

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