Rational design of a reactive yet stable organic-based photocatalyst

Gerdes, Robert; Łapok, Łukasz; Tsaryova, Olga; Wöhrle, Dieter; Gorun, Sergiu M.

doi:10.1039/b822111c

Cited by 45 publications

(48 citation statements)

References 22 publications

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“…2a) produces 1 O 2 in a relatively high quantum yield232425. Unlike the protio phthalocyanine, H 16 PcZn, F 64 PcZn is stable in the presence of 1 O 2 and daughter, oxygen-centered species and other radicals2627. The bulky i -C 3 F 7 groups of F 64 PcZn effectively protect this molecule from aggregation and facilitate its dissolution in organic solvents such as ethanol.…”

Section: Resultsmentioning

confidence: 99%

Singlet oxygen-based electrosensing by molecular photosensitizers

et al. 2017

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Enzyme-based electrochemical biosensors are an inspiration for the development of (bio)analytical techniques. However, the instability and reproducibility of the reactivity of enzymes, combined with the need for chemical reagents for sensing remain challenges for the construction of useful devices. Here we present a sensing strategy inspired by the advantages of enzymes and photoelectrochemical sensing, namely the integration of aerobic photocatalysis and electrochemical analysis. The photosensitizer, a bioinspired perfluorinated Zn phthalocyanine, generates singlet-oxygen from air under visible light illumination and oxidizes analytes, yielding electrochemically-detectable products while resisting the oxidizing species it produces. Compared with enzymatic detection methods, the proposed strategy uses air instead of internally added reactive reagents, features intrinsic baseline correction via on/off light switching and shows C-F bonds-type enhanced stability. It also affords selectivity imparted by the catalytic process and nano-level detection, such as 20 nM amoxicillin in μl sample volumes.

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Section: Resultsmentioning

confidence: 99%

Singlet oxygen-based electrosensing by molecular photosensitizers

et al. 2017

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“…Consequently, triplet photosensitizers are utilized as triplet energy donors to initiate either photochemical reactions or induce photophysical processes in another molecular entity . Triplet photosensitizers have been considered for a variety of applications, such as phosphorescent materials, phosphorescent bioimaging, chemosensors, photoinitiators of polymerization, photocatalysts (e.g., for photoinduced hydrogen production from water), triplet–triplet annihilation‐based upconversion (TTAU), oxygen sensors, and initiators of photoredox organic reactions . Furthermore, triplet photosensitizers have found use in oncological and antibacterial photodynamic therapy (PDT) to eradicate cancerous cells or pathogens, respectively .…”

Section: Introductionmentioning

confidence: 99%

Facile Synthesis, Triplet‐State Properties, and Electrochemistry of Hexaiodo‐Subphthalocyanine

Obłoza

Łapok

Solarski

et al. 2018

Chemistry A European J

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In view of the ever-growing demand for efficient triplet photosensitizers and photoactive components of various optoelectronic devices, we herein report the synthesis and properties of hexaiodo-subphthalocyanines (I SubPcs). The improved five-step route to 4,5-diiodophthalonitrile, which serves as precursor for the synthesis of the I SubPcs, is reported. The improved synthesis merely required one chromatographic separation to afford the high-purity target product. Highly desirable photophysical and photochemical properties were induced in the I SubPcs due to the presence of six heavy iodine atoms. In particular, high values of the singlet-oxygen quantum yields (Φ ) ranging from 0.83 to 0.9 were measured. The I SubPcs investigated proved to be phosphorescent at 77 K in 2-MeTHF with emission band maxima (λ ) located at λ=957 and 970 nm. The excited-triplet-state energies (E ) were estimated to be approximately 1.30 eV, whereas the triplet lifetimes (τ ) were found to be 27.7 and 30.1 μs. The CV/DPV measurements indicated that both I SubPcs exhibited one irreversible oxidation and one quasi-reversible reduction. The spectroelectrochemical measurements pointed to a relative stability and reversibility of the electrochemically formed anion radical, that is, I SubPc , and an instability of the species formed upon one-electron oxidation, that is, I SubPc . Estimation of E gave a value of approximately -5.8 eV whereas E was found to be located at around -3.8 eV.

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“…So far,m etals such as Zn II ,C o II ,Mg II ,Fe II ,Ru II ,V = O, Tb, and Lu have been successfully incorporated into the PcF 64 scaffold. [16][17][18][19][20][21][22] The three-step procedure leadingt oc ompounds PdPcF 64 4 and PtPcF 64 5 is presented in Scheme1.S ynthesis of palladium(II) and platinum(II) complexes 4 and 5 started with the synthesis of perfluoro(4,5-diisopropyl)phthalonitrile (2)b ased on ap reviously described procedure. [23] Treatmento f am ethanolic solution of 2 with ammonia gas at room temperature afforded 1,3-diiminoisoindoline 3 in quantitative yield.…”

Section: Synthesis and Characterizationmentioning

confidence: 99%

“…Ak nown strategyf or fine-tuning of the emissive properties is through the effect exerted by the substituents.I ng eneral, electronwithdrawing substituents tend to stabilize the HOMO by diminishing electron density at the metal, resulting in ablueshift, whereas electron-donatings ubstituents act inversely. 1,4,8,11,15,18,22,3,9,10,16,17,23,octaperfluoroisopropyl-phthalocyanine ligand provides an extreme example of this effect because it probably constitutes the most electron-withdrawingl igand known (64 Fatoms per ligand).…”

Section: Introductionmentioning

confidence: 99%

Near Infrared Phosphorescent, Non‐oxidizable Palladium and Platinum Perfluoro‐phthalocyanines

et al. 2016

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New Pd(II) and Pt(II) complexes with a highly electron-deficient ligand (H2 PcF64 ) were conveniently prepared in a three-step synthesis. This is the first time that the phosphorescence of phthalocyanines with a H2 PcF64 framework has been measured. Based on these measurements, the triplet-state energies (ET ) were directly determined. Transient absorption experiments revealed broad T1 →Tn absorption spanning from ca. 350 to ca. 1000 nm and allowed determination of the triplet-state lifetimes. Removal of the Pd or Pt from the perfluoro-phthalocyanine resulted in a significant increase of the triplet lifetime for H2 PcF64 . The very efficient intersystem crossing observed for both PdPcF64 and PtPcF64 leads to residual fluorescence and suppresses the fluorescence lifetimes to less than 50 ps. The absence of Pd and Pt in the perfluoro-phthalocyanine ligand, viz. H2 PcF64 , led to a recovery of fluorescence. Cyclic voltamperometry studies pointed to complete resistance of PdPcF64 and PtPcF64 to oxidation and very strong electron affinity, which rendered these materials very good electron acceptors (n-type materials). The presence of d-orbital metals such as Pd(II) and Pt(II) in the phthalocyanine ring stabilizes their reduced forms, as indicated by the spectroelectrochemical experiments. PdPcF64 and PtPcF64 easily sensitize singlet oxygen production with very high quantum yields. Both phthalocyanines presented resistance to photodegradation in the solid state under aerobic conditions and under intense irradiation.

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Rational design of a reactive yet stable organic-based photocatalyst

Cited by 45 publications

References 22 publications

Singlet oxygen-based electrosensing by molecular photosensitizers

Singlet oxygen-based electrosensing by molecular photosensitizers

Facile Synthesis, Triplet‐State Properties, and Electrochemistry of Hexaiodo‐Subphthalocyanine

Near Infrared Phosphorescent, Non‐oxidizable Palladium and Platinum Perfluoro‐phthalocyanines

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