176446-62-1Relevant articles and documents
Synergic effect on oxygen reduction reaction of strapped iron porphyrins polymerized around carbon nanotubes
Hanana, Manel,Arcostanzo, Hélène,Das, Pradip K.,Bouget, Morgane,Le Gac, Stéphane,Okuno, Hanako,Cornut, Renaud,Jousselme, Bruno,Dorcet, Vincent,Boitrel, Bernard,Campidelli, Stéphane
, p. 19749 - 19754 (2018)
In the context of the development of new bio-inspired catalysts, MN4 complexes exhibit a great potential for small molecule activation. In particular, metallated porphyrins and phthalocyanines combined with carbon nanotubes have been tested for the oxygen reduction reaction in electrocatalytic systems, and these nanotube/MN4 hybrids have demonstrated promising properties. Here, a series of hybrid materials made of multi-walled carbon nanotubes (MWNTs) coated with strapped porphyrins have been fabricated. Iron porphyrin derivatives were polymerized around the nanotubes via Hay coupling and the resulting materials were fully characterized. Two porphyrins were probed; both were strapped with the same skeleton and they differed only in the presence or absence of overhung carboxylic acids. In the porphyrin, the carboxylic acid group could possibly act as a proton relay between the medium and the catalyst. Although the presence of the carboxylic acid groups (acting as intramolecular proton relays) did not exhibit a significant influence on the catalytic properties, the combination of both components-the MWNTs and porphyrin-led to a better catalytic activity than those of the nanotubes or the porphyrins taken separately. The synergic affect is due to the MWNTs which ensure the availability of electrons to the porphyrin catalysts and allow the ORR to occur via the 4-electron pathway, avoiding the production of hydrogen peroxide.
Amino Acid-Porphyrin Conjugates: Synthesis and Study of their Photophysical and Metal Ion Recognition Properties
Paul, Albish K.,Karunakaran, Suneesh C.,Joseph, Joshy,Ramaiah, Danaboyina
, p. 1348 - 1355 (2015)
Synthesis, photophysical and metal ion recognition properties of a series of amino acid-linked free-base and Zn-porphyrin derivatives (5-9) are reported. These porphyrin derivatives showed favorable photophysical properties including high molar extinction coefficients (>1 × 105 m-1 cm-1 for the Soret band), quantum yields of triplet excited states (63-94%) and singlet oxygen generation efficiencies (59-91%). Particularly, the Zn-porphyrin derivatives, 6 and 9 showed higher molar extinction coefficients, decreased fluorescence quantum yields, and higher triplet and singlet oxygen quantum yields compared to the corresponding free-base porphyrin derivatives. Further, the study of their interactions with various metal ions indicated that the proline-conjugated Zn-porphyrins (6 and 9) showed high selectivity toward Cu2+ ions and signaled the recognition through changes in fluorescence intensity. Our results provide insights on the role of nature of amino acid and metallation in the design of the porphyrin systems for application as probes and sensitizers.
Quantitative Structure-Property Relationship Modelling for the Prediction of Singlet Oxygen Generation by Heavy-Atom-Free BODIPY Photosensitizers**
Buglak, Andrey A.,Charisiadis, Asterios,Sheehan, Aimee,Kingsbury, Christopher J.,Senge, Mathias O.,Filatov, Mikhail A.
supporting information, p. 9934 - 9947 (2021/05/31)
Heavy-atom-free sensitizers forming long-living triplet excited states via the spin-orbit charge transfer intersystem crossing (SOCT-ISC) process have recently attracted attention due to their potential to replace costly transition metal complexes in photonic applications. The efficiency of SOCT-ISC in BODIPY donor-acceptor dyads, so far the most thoroughly investigated class of such sensitizers, can be finely tuned by structural modification. However, predicting the triplet state yields and reactive oxygen species (ROS) generation quantum yields for such compounds in a particular solvent is still very challenging due to a lack of established quantitative structure-property relationship (QSPR) models. In this work, the available data on singlet oxygen generation quantum yields (ΦΔ) for a dataset containing >70 heavy-atom-free BODIPY in three different solvents (toluene, acetonitrile, and tetrahydrofuran) were analyzed. In order to build reliable QSPR model, a series of new BODIPYs were synthesized that bear different electron donating aryl groups in the meso position, their optical and structural properties were studied along with the solvent dependence of singlet oxygen generation, which confirmed the formation of triplet states via the SOCT-ISC mechanism. For the combined dataset of BODIPY structures, a total of more than 5000 quantum-chemical descriptors was calculated including quantum-chemical descriptors using density functional theory (DFT), namely M06-2X functional. QSPR models predicting ΦΔ values were developed using multiple linear regression (MLR), which perform significantly better than other machine learning methods and show sufficient statistical parameters (R=0.88–0.91 and q2=0.62–0.69) for all three solvents. A small root mean squared error of 8.2 % was obtained for ΦΔ values predicted using MLR model in toluene. As a result, we proved that QSPR and machine learning techniques can be useful for predicting ΦΔ values in different media and virtual screening of new heavy-atom-free BODIPYs with improved photosensitizing ability.
Physicochemical and computational insight of 19F NMR and emission properties of: Meso -(o -aryl)-BODIPYs
Farfán-Paredes, Mónica,González-Antonio, Oscar,Tahuilan-Anguiano, Diana E.,Peón, Jorge,Ariza, Armando,Lacroix, Pascal G.,Santillan, Rosa,Farfán, Norberto
, p. 19459 - 19471 (2020/12/04)
A series of electronic and physicochemical parameters were explored to determine their effect on experimental spectroscopic and photophysical data. Through a systematic obtention of a series of meso-(o-aryl)-BODIPYs, 19F NMR spectra were analyzed and thei
