A leopard cannot change its spots: Unexpected products from the vilsmeier reaction on 5,10,15-tritolylcorrole

The reaction of 5,10,15-tritolylcorrole with 3-dimethylaminoacrolein (3-DMA) and POCl3 gives a further example of the rebel reactivity of this contracted macrocycle. While no evidence was obtained for the formation of the expected -acrolein corrole, the inner core substituted N21,N22-3-formylpropylcorrole and the 10-acrolein isocorrole were the reaction products. By increasing the temperature or the amount of the Vilsmeier reagent, the 10-isocorrole became the unique reaction product. The formation of the isocorrole by electrophilic attack of the Vilsmeier reagent to the 10-position of the corrole is unprecedented in the porphyrinoids field and it could pave the way for a novel route to the preparation of stable isocorrole

Panchromatic light harvesting and stabilizing charge-separated states in corrole–phthalocyanine conjugates through coordinating a subphthalocyanine

Owing to the electron-donating and -accepting nature of corroles (Corr) and phthalocyanines (Pc), respectively, we designed and developed two novel covalently linked Corr-Pc conjugates. The synthetic route allows the preparation of the target conjugates in satisfying yields. Comprehensive steady-state absorption, fluorescence, and electrochemical assays enabled insights into energy and electron-transfer processes upon photoexcitation. Coordinating a pyridine-appended subphthalocyanine (SubPc) to the Pc of the conjugate sets up the ways and means to realize the first example of an array composed by three different porphyrinoids, which drives a cascade of energy and charge-transfer processes. Importantly, the SubPc assists in stabilizing the charge-separated state, that is, one-electron oxidized Corr and the one electron-reduced Pc, upon photoexcitation by means of a reductive charge transfer to the SubPc. To the best of our knowledge, this is the first case of an intramolecular oxidation of a Corr within electron-donor–acceptor conjugates by means of just photoexcitation. Moreover, the combination of Corr, Pc, and SubPc guarantees panchromatic absorption across the visible range of the solar spectrum, with the SubPc covering the „green gap“ that usually affects porphyrinoids

All-solid-state paper based potentiometric potassium sensors containing Cobalt(II) porphyrin/Cobalt(III) corrole in the transducer layer

Disposable ion-selective electrodes of high reproducibility of recorded potentials between different sensors have been prepared using carbon-nanotubes modified paper as the transducer and electrical lead, and a poly(vinyl chloride) ion-selective membrane. The conducting paper was obtained using carboxymethylcellulose stabilized carbon nanotubes suspension – combination found to result in high stability of conventional sensors. It was shown for the first time that change of the amount of conducting material used to prepare sensor, from conventional (where it is used as transducer) to disposable sensors (where it is used as transducer and electrical lead), requiring application of much higher amount of carbon nanotubes significantly affects performance of the sensors. Presence of ions in the suspension used results in occurrence of super-Nernstian range on the potentiometric calibration curve of potassium-selective sensor, below 10−5 M KCl. Highly reproducible potential values, between sensors as well as between different calibrations, were achieved introducing mixture of cobalt(II) porphyrin/cobalt(III) corrole to the carbon nanotubes layer, at the back side of the membrane. Presence of porphyrinoids not only stabilizes potential values obtained for the sensors but also tailors ion transport through the membrane, resulting in stable potential of the sensors, although a super-Nernstian region is present on the calibration line. © 2018 Elsevier B.V

Panchromatic light harvesting and stabilizing charge-separated states in corrole–phthalocyanine conjugates through coordinating a subphthalocyanine

Owing to the electron-donating and -accepting nature of corroles (Corr) and phthalocyanines (Pc), respectively, we designed and developed two novel covalently linked Corr-Pc conjugates. The synthetic route allows the preparation of the target conjugates in satisfying yields. Comprehensive steady-state absorption, fluorescence, and electrochemical assays enabled insights into energy and electron-transfer processes upon photoexcitation. Coordinating a pyridine-appended subphthalocyanine (SubPc) to the Pc of the conjugate sets up the ways and means to realize the first example of an array composed by three different porphyrinoids, which drives a cascade of energy and charge-transfer processes. Importantly, the SubPc assists in stabilizing the charge-separated state, that is, one-electron oxidized Corr and the one electron-reduced Pc, upon photoexcitation by means of a reductive charge transfer to the SubPc. To the best of our knowledge, this is the first case of an intramolecular oxidation of a Corr within electron-donor–acceptor conjugates by means of just photoexcitation. Moreover, the combination of Corr, Pc, and SubPc guarantees panchromatic absorption across the visible range of the solar spectrum, with the SubPc covering the „green gap“ that usually affects porphyrinoidsFinancial support from Spanish MICINN (CTQ2017-85393-P) and Italian MIUR (Sunset PRIN 2017EKCS35 002) is acknowledged. IMDEA Nanociencia acknowledges support from the “Severo Ochoa” Programme for Centres of Excellence in R&D (MINECO, Grant SEV2016-0686). Open access funding enabled and organized by Projekt DEA

β-Pyrrolopyrazino Annulated Corroles via a Pictet–Spengler Approach

Reaction of 2-amino-3-(pyrrol-1-yl)-5,10,15-tris(4-tert-butylphenyl)corrolato copper(II) with arylaldehydes affords novel π-extended β,β′-pyrrolo(1,2-a)pyrazino-fused corroles via a Pictet–Spengler reaction. Corrole shows an unprecedented reaction pathway, leading to a mixture of phenyl-substituted and nonsubstituted pyrrolopyrazino annulated species as reaction products

Grafting corroles onto ZnO nanoparticles

Two different copper and gallium arylcorroles have been functionalized using the Vilsmeier–Haack reaction. A further Knoevenagel reaction with cyanoacetic acid was performed on both complexes, affording the desired products with yields above 90 %. The newly synthesized compounds have been thoroughly characterized by a combination of spectroscopic methods, optical analyses, and X-ray crystallography. Moreover, they have been tested as anchoring groups for the hydrothermal synthesis of ZnO nanoparticles. The morphology of the heterogeneous composites has been studied by SEM, EDS and fluorescence microscopy analyses, thus confirming the presence of the corrole macrocycle in the hybrid material. © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinhei

Copper-based corrole as thermally stable hole transporting material for perovskite photovoltaics

Perovskite solar cells (PSCs) represent nowadays a promising starting point to develop a new efficient and low-cost photovoltaic technology due to the demonstrated power conversion efficiency (PCE) exceeding 25% on small area devices. However, best reported devices suffer from stability issue under real working conditions thus slowing down the race for the commercialization. In particular, the hole transporting material commonly employed in mesoscopic n–i–p PSCs (nip-mPSCs), namely spiro-OMeTAD, is strongly corrupted when subjected to temperatures above 70 °C due to intrinsic thermal instability and because of the dopant employed to improve the hole mobility. In this work, the novel use of a copper-based corrole as HTM is proposed to improve the device thermal stability of nip-mPSCs under prolonged 85 °C stress conditions. Corrole-based devices show remarkable PCE above 16% by retaining more than 65% of the initial PCE after 1000 h of thermal stress, while spiro-OMeTAD cells abruptly lose more than 60% after the first 40 h. Once scaled-up to large area modules, the proposed device structure can truly represent a possible way to pass thermal stress tests proposed by IEC-61646 standards and, not less importantly, the high temperature required by the lamination process for panel production

β-Arylethynyl substituted silver corrole complexes

Silver corrolates are attractive compounds from both practical and theoretical points of view. Indeed, they play a key role in peripheral functionalization reactions occurring at the macrocycle, enabling high-yield and regioselective group insertions useful to further elaborate the molecular skeleton. In parallel, the Janus innocent or noninnocent behavior of the corrole ligand in these complexes makes their description particularly challenging. Herein, we report properties for a series of silver 3,17-disubstituted triarylcorrole complexes with various functionalities (halogens or different phenylethynyl units) that deeply affect the electron density in the macrocyclic ligand, with obvious repercussions on the observed spectral characteristics. The compounds were obtained in yields of 54-92% by applying the Stille coupling reaction with the appropriate tributylethynyl stannane. Among the complexes prepared was a derivative bearing two terminal acetylenic units which opens the way to "click" reactions for new corrole-based architectures. This corrole was structurally characterized by single crystal X-ray crystallography. The addition of substituted ethynyl groups resulted in red-shifts of the electronic absorption spectra, the largest of which was observed for the compound with two beta-NO2-Ph-C & xe002;C substituents. The remarkable influence of the NO2 groups on the electron density of this macrocycle was further demonstrated by electrochemical measurements, where an easier reduction of this complex derivative was observed as compared to the others. DFT calculations showed full delocalization over the entire p-nitrophenylethynyl unit of 5, largely affecting orbital distributions and the corresponding electronic absorptions. Although a variation of the beta-substituents dramatically modifies the Soret- and Q-band positions towards lower energies for all the examined complexes, the saddling of the macrocycle resulting from functionalization is only moderate. The collected results suggest the description of these compounds as Ag-III-corrolate(3-), a metallocorrole with an innocent macrocyclic ligand