Nonfullerene Polymer Solar Cells Reaching a 9.29% Efficiency Using a BODIPY-Thiophene Backboned Donor Material

A conjugated polymer donor containing BODIPY-thiophene dyads in the backbone, P(BdP-EHT), combined with a low bandgap nonfullerene acceptor (SMDPP) consisting of carbazole and diketopyrrolopyrrole units linked with a tetracyanobutadiene acceptor π-linker, was used to design bulk heterojunction polymer solar cells. After the optimization of the donor to acceptor weight ratio and solvent vapor annealing of the P(BdP-EHT):SMDPP active layer, the resulting polymer solar cell showed an overall power conversion efficiency of 9.29%, which is significantly higher than that for the polymer solar cell based on PC71BM (7.41%) processed under identical conditions. This improved power conversion efficie…

The first example of cofacial bis(dipyrrins)

International audience; Two series of cofacial bis(dipyrrins) were prepared and their photophysical properties as well as their bimolecular fluorescence quenching with C-60 were investigated. DFT and TDDFT computations were also performed as a modeling tool to address the nature of the fluorescence state and the possible inter-chromophore interactions. Clearly, there is no evidence for such interactions and the bimolecular quenching of fluorescence, in comparison with mono-dipyrrins, indicates that C-60-bis(dipyrrin) contacts occur from the outside of the "mouth" of the cofacial structure.

Surface Acoustic Wave Sensors for the Detection of Hazardous Compounds in Indoor Air

Presented at the Eurosensors 2017 Conference, Paris, France, 3–6 September 2017.; International audience; In this work, the authors show the capabilities of Surface Acoustic Wave (SAW) devices coupled with various absorbents to probe the properties of gas sensitive materials for the manufacturing of hazardous gas sensors. The great capabilities of cobalt corroles for the trapping of carbon monoxide (CO) were exploited to produce selective sensors. These corroles were deposited on SAW delay lines surfaces and then exposed to carbon monoxide (CO) in standard conditions. Concentrations of a few hundreds of ppb were measured emphasizing the interest of such sensors for the detection of CO. Anot…

Easy access to heterobimetallic complexes for medical imaging applications via microwave-enhanced cycloaddition

The Cu(I)-catalysed Huisgen cycloaddition, known as “click” reaction, has been applied to the synthesis of a range of triazole-linked porphyrin/corrole to DOTA/NOTA derivatives. Microwave irradiation significantly accelerates the reaction. The synthesis of heterobimetallic complexes was easily achieved in up to 60% isolated yield. Heterobimetallic complexes were easily prepared as potential MRI/PET (SPECT) bimodal contrast agents incorporating one metal (Mn, Gd) for the enhancement of contrast for MRI applications and one “cold” metal (Cu, Ga, In) for future radionuclear imaging applications. Preliminary relaxivity measurements showed that the reported complexes are promising contrast agent…

Two-Photon Absorption Properties and Structures of BODIPY and Its Dyad, Triad and Tetrad.

A series consisting of a dyad, a triad and a tetrad containing either two, three and four BODIPY units, respectively, has been synthesized and fully characterized and compared to two mono-BODIPY analogs (used as references). The one- and two-photon photophysical properties have been measured and the X-ray structures of four of the BODIPY derivatives have been determined. In the 700-900 nm range, the two-photon absorption (TPA) cross sections range from 30 GM to 160 GM for these compounds.

Random Structural Modification of a Low-Band-Gap BODIPY-Based Polymer

International audience; A BODIPY thiophene polymer modified by extending conjugation of the BODIPY chromophore is reported. This modification induces tunability of energy levels and therefore absorption wavelengths in order to target lower energies.

Antipoxvirus Activity Evaluation of Optimized Corroles Based on Development of Autofluorescent ANCHOR Myxoma Virus

International audience; A series of 43 antiviral corrole-based molecules have been tested on myxoma virus (Lausanne-like T1MYXV strain). An autofluorescent MYXV, with an ANCHOR cassette, has been used for the studies. A(2)B-fluorocorroles display various toxicities, from 40 being very toxic (CC50 = 1.7 mu M) to nontoxic 38 (CC50 > 50 mu M), whereas A(3)-fluorocorroles, with one to three fluorine atoms, are not toxic (with the exception of corroles 9, 10, and 22). In vitro, these compounds show a good selectivity index when used alone. Corrole 35 seems to be the most promising compound, which displays a high selectivity index with the lowest IC50. Interestingly, this "Hit" corrole is easy to…

Synthesis, Electrochemistry, and Photophysics of Aza-BODIPY Porphyrin Dyes

International audience; The synthesis of dyad and triad aza-BODIPY-porphyrin systems in two steps starting from an aryl-substituted aza-BODIPY chromophore is described. The properties of the resulting aza-BODIPY-porphyrin conjugates have been extensively investigated by means of electrochemistry, spectroelectrochemistry, and absorption/emission spectroscopy. Fluorescence measurements have revealed a dramatic loss of luminescence intensity, mainly due to competitive energy transfer and photoinduced electron transfer involving charge separation followed by recombination.

Electrochemical and Spectroelectrochemical Properties of Free-Base Pyridyl- and N -Alkyl-4-Pyridylporphyrins in Nonaqueous Media

International audience; Twelve structurally related pyridyl and meso-N-methylpyridylporphyrin derivatives are investigated electrochemically in different nonaqueous media. The UV/Vis spectrum of each newly investigated porphyrin was measured before and after electro-reduction and, based on this data, the site of electron transfer is proposed. An interaction occurs between the meso-pyridyl or meso-N-alkyl-4-pyridyl substituents and the porphyrin p-ring system, the magnitude of which depends upon the number of linked pyridyl or N-alkyl-4-pyridyl groups in the compound, the solvent, the supporting electrolyte, and/or other anions added to the solution.

cis-Dichloroplatinum(II) complexes tethered to dibenzo[c,h][1,6]naphthyridin-6-ones: Synthesis and cytotoxicity in human cancer cell lines in vitro

A novel family of cisplatin-type complexes tethered to dibenzo[c,h][1,6]naphthyridin-6-one topoisomerase inhibitor via a polymethylene chain and their nonplatinated counterparts were prepared. Their potential cytotoxicity was assessed in three human colorectal cancer cell lines HCT 116, SW480 and HT-29 and compared to the reference molecules cisplatin and oxaliplatin. Platinated compounds were poorly active whilst nonplatinated dibenzo[c,h][1,6]naphthyridin-6-one moieties exhibited higher cytotoxic properties than cisplatin and oxaliplatin whatever the length of the polymethylene chain; molecules containing the tri- and hexamethylene chain length were the most cytotoxic.

Synthesis, Characterization, and Electrochemistry of Open-Chain Pentapyrroles and Sapphyrins with Highly Electron-Withdrawing meso -Tetraaryl Substituents

International audience; A series of open-chain pentapyrroles and sapphyrins with highly electron-withdrawing substituents (i.e., CN, CF3 , or CO2 Me) on the meso-phenyl rings was synthesized and characterized as to the spectral properties, protonation reactions, and electrochemistry in non-aqueous media. The investigated compounds are represented as (Ar)4 PPyH3 and (Ar)4 SapH3 where PPy and Sap correspond to the tri-anion of the open-chain pentapyrrole and sapphyrin, respectively, and Ar=p-CNPh, p-CF3 Ph, or p-CO2 MePh. UV/Vis and 1 H NMR spectroscopy as well as mass spectrometry data are given for the confirmation of the structures for the newly synthesized compounds. An X-ray structure fo…

Porous materials applied to biomarker sensing in exhaled breath for monitoring and detecting non-invasive pathologies

International audience; Overview of the use of porous materials for gas sensing to analyze the exhaled breath of patients for disease identification.The quantification of specific gases among thousand of VOCs (Volatile Organic Compounds) present in the human breath at the ppm/ppb level can be used to evidence the presence of diseases in the human body. The detection of these biomarkers in human exhaled breath through a noninvasive approach is an important field of research which is still attracting important attention to this day. A portable device working at room temperature and usable directly on exhaled breath samples is still a challenge requiring a sensing material with high performanc…

Cobalt Corroles with Bis‐Ammonia or Mono‐DMSO Axial Ligands. Electrochemical, Spectroscopic Characterizations and Ligand Binding Properties

International audience; Four bis-ammonia ligated cobalt corroles and four mono-DMSO ligated cobalt corroles with different mesoaryl substituents on the macrocycle (A 2 Band A 3-corroles) were synthesized and investigated as to their electrochemical and spec-troscopic properties under different solution conditions. The complexation energies of the investigated cobalt corroles were theoretically calculated to illustrate the propensity of the cobalt center for pentacoordination or hexa-coordination with various axial ligands (DMSO, CO, py and NH 3). The structure of one hexacoordinate bis-NH 3 cobalt corrole complex was also determined by X-ray diffraction.

A bacteriochlorin-diketopyrrolopyrrole triad as a donor for solution-processed bulk heterojunction organic solar cells

We have designed an A–π–D–π–A small-molecule triad consisting of a bacteriochlorin (BC) donor central core linked with two diketopyrrolopyrrole (DPP) acceptors via ethynyl bridges (BC-DPP-1). BC-DPP-1 has a narrow optical bandgap of 1.38 eV with highest occupied molecular orbital and lowest unoccupied molecular orbital energy levels of −4.93 eV and −3.40 eV, respectively, and it was used as an electron donor along with [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) as an acceptor for solution-processed small-molecule organic solar cells. After optimizing the weight ratio between BC-DPP-1 and PC71BM and pyridine as a solvent additive and subsequent solvent vapor annealing using THF, an …

Synthesis, electrochemistry, protonation and X-ray analysis of meso-aryl substituted open-chain pentapyrroles

Five meso-tetraaryl open-chain pentapyrroles were synthesized and characterized as to their electrochemistry and protonation reactions in nonaqueous media. The investigated compounds are represented as (Ar)4PPyH3 where Ar [Formula: see text],[Formula: see text]-F2Ph, [Formula: see text]-BrPh, Ph, [Formula: see text],[Formula: see text],[Formula: see text]-(OMe)3Ph or [Formula: see text]-MePh and were characterized by UV-vis and 1H NMR spectroscopy, mass spectrometry and electrochemistry. Cyclic voltammetry was used to measure redox potentials, while protonation involving the conversion of (Ar)4PPyH3 to [(Ar)4PPyH5][Formula: see text] was monitored by UV-vis absorption spectroscopy. Equilib…

Non-linear optical, electrochemical and spectroelectrochemical properties of amphiphilic inner salt porphyrinic systems

Three zwitterionic meso-substituted A3B- and AB2C-porphyrins containing one sulfonato alkylpyridinium substituent and three or two alkoxy-substituted phenyl groups were synthesized in good yield and fully characterized as to their physicochemical properties by a variety of techniques. This new series of inner salt donor-acceptor meso-substituted porphyrin derivatives were prepared for possible application as amphiphilic probes for membrane insertion in the area of combined second-harmonic and two-photon fluorescence cellular microscopy. To this end, the linear and nonlinear optical properties of the compounds were characterized, together with their electrochemical and spectroelectrochemica…

Covalent Organic Frameworks for the detection of CO

International audience; Every year in the world, carbon monoxide (CO) is responsible for thousands of intoxications and hundreds of deaths. The detection (CO) at few ppm levels is thus a critical point for the control of the air quality. Corrole belongs to the family of porphyrinoids which is largely used for sensing applications [1]. We have shown that cobalt metallocorroles are able to bind carbon monoxide in the axial position with a high affinity even in the presence of nitrogen and dioxygen, the two main components of the atmosphere [2]. We have recently prepared sensing devices for low CO detection level (sub-ppm) using cobalt corroles deposited as films on a Surface Acoustic Wave dev…

Tuning the Electrochemistry of Free-Base Porphyrins in Acidic Nonaqueous Media: Influence of Solvent, Supporting Electrolyte, and Ring Substituents

International audience; A detailed study of reduction potentials, electroreduction mechanisms and acid-base chemistry was carried out on two series of free-base porphyrins in nonaqueous media. The first series is represented by four-pyrrole substituted tetraphenylporphyrin (TPP) derivatives, two of which are planar and two of which are nonplanar in their non-protonated form. The second comprises porphyrins with 0-4 meso-phenyl groups on the macrocycle. Equilibrium constants for conversion of each neutral porphyrin to its diprotic [H4P] 2+ form were determined and the electrochemistry was then elucidated as a function of: (i) type of nonaqueous solvent, (ii) anion of supporting electrolyte, …

Design of Porphyrin-dota-Like Scaffolds as All-in-One Multimodal Heterometallic Complexes for Medical Imaging

A series of four multimodal ligands incorporating one porphyrin moiety and one or more dota-like macrocycles all-in-one in the same molecular architecture have been synthesized and full characterized. The corresponding gadolinium(III) complexes were also synthesized and heterometallic complexes incorporating both gadolinium(III) and copper(II) ions were prepared as potential MRI/PET multimodal contrast agents. One ligand (L4) includes an amine moiety that can be activated for easy conversion into an isothiocyanate group for further anchoring to a biological vector. Preliminary relaxivity, cytotoxicity, and MRI studies showed that the complexes developed in this work are very promising medic…

Polymer solar cell based on ternary active layer consists of medium bandgap polymer and two non-fullerene acceptors

Abstract An efficient PSCs consisting of a ternary active layer containing a medium bandgap conjugated polymer P and two well-known non-fullerene acceptors i.e. ITIC-m and Y6 was fabricated. An overall Power Conversion Efficiency (PCE) of about 15.13% was achieved, with the optimized ternary active layer consisting of 20 wt% of ITIC-m in acceptors i.e. P:ITIC-m:Y6 (1:0.3:1.2). This value is higher than that for the binary counter parts i.e. 12.10% and 13.16% for P:ITIC-m (1:1.5 w:w) and P:Y6 (1:1.5 w:w). The higher short circuit current density of the ternary active layer PSCs is related to the broader absorption spectra as compared to the binary active layer analogs. The open circuit volta…

Inside Cover: Synthesis and Characterization of Carbazole-Linked Porphyrin Tweezers (Chem. Eur. J. 34/2015)

Synthesis and Antiviral Activity Evaluation of Nitroporphyrins and Nitrocorroles as Potential Agents against Human Cytomegalovirus Infection.

Different nitroporphyrinoid derivatives were synthesized and studied as potential agents against human Cytomegalovirus. Interestingly, two nitrocorroles display strong activity against human Cytomegalovirus with IC 50 < 0.5 μM. These compounds also possess antiproliferative activities without detected in vivo toxicity. Therefore, nitrocorroles appear for the first time as potential active compounds that can be applied in human health.

Synthetic strategy for preparation of a folate corrole DOTA heterobimetallic Cu–Gd complex as a potential bimodal contrast agent in medical imaging

Abstract An efficient sequential route to synthesize heterobimetallic complexes is reported herein. A folate, Cu corrole, Gd DOTA complex that addresses the requirements of a potential contrast agent (CA) for bimodal imaging (e.g., MRI/PET) is reported. The over-expression of the folate receptor in a variety of malignant tumors, along with its limited expression in healthy tissues, makes this an attractive tumor-specific molecular target. Synthesis of a bimetallic ligand potentially targeting the folate receptor, was easily achieved in only a few steps. Interestingly, preliminary studies showed that the relaxivity of the folic heterobimetallic derivative was higher in comparison to a clinic…

Porphyrins and BODIPY as Building Blocks for Efficient Donor Materials in Bulk Heterojunction Solar Cells

International audience; Advances in the synthesis and application of highly efficient polymers and small molecules over the last two decades have enabled the rapid advancement in the development of organic solar cells and photovoltaic technology as a promising alternative to conventional solar cells, based on silicon and other inorganic semiconducting materials. Among the different types of organic semiconducting materials, porphyrins and BODIPY-based small molecules and conjugated polymers attract high interest as efficient semiconducting organic materials for dye sensitized solar cells and bulk heterojunction organic solar cells. The highest power conversion efficiency exceeding 9% has be…

Photovoltaic Properties of a Porphyrin-Containing Polymer as Donor in Bulk Heterojunction Solar Cells With Low Energy Loss

BODIPY–diketopyrrolopyrrole–porphyrin conjugate small molecules for use in bulk heterojunction solar cells

Two small molecules denoted as BD-pPor and BD-tPor composed of a central BODIPY core surrounded with two DPP and two porphyrin units have been designed and synthesized. In BD-pPor and BD-tPor, porphyrins are linked to the central BODIPY by phenyl and thiophene bridges, respectively. The optical and electrochemical properties were systematically investigated in order to employ them as donors along with PC71BM as an acceptor for solution processed bulk heterojunction organic solar cells. After the optimization of the active layer, the organic solar cells based on BD-pPor and BD-tPor exhibit overall power conversion efficiencies of 6.67% and 8.98% with an energy loss of 0.63 eV and 0.50 eV. Th…

Synthesis of Polyfused Heterocycle Derivatives Containing the Dipyridoimidazole Core by Friedländer’s Reaction: Access to Analogs of Ellipticine

Reaction of 3-amino-2-formylimidazo[l,2-a]pyridine with various aldehydes and ketones by Friedlander's methodology afforded an entry to dipyridoimidazole, tri(tetra)azacyclopenta[b]fluorene, tri(tetra)azabenzo[b]-fluorene and triazaindeno[2,1-b]phenanthrene derivatives. Intercalation with a synthetic oligodeoxynucleotide was examined.

Tetracationic and Tetraanionic Manganese Porphyrins: Electrochemical and Spectroelectrochemical Characterization

International audience; The electrochemistry and spectroelectrochemistry of four tetrapositively charged and two tetranegatively charged porphyrins were characterized in two nonaqueous solvents (dimethyl sulfoxide and N,N-dimethylformamide) containing 0.1 M tetra-n-butylammonium perchlorate. The tetrapositively charged compounds are represented by the tetrapyridylporphyrins [TRPyPM]4+(X-)4, where R is a methyl or [2-[2-(2-methoxy)ethoxy]ethoxy]ethyl group, M = MnIIII, MnIIICl, CuII, or PdII, and X = I- or Cl-. The tetranegatively charged porphyrins are represented by the tetrasulfonato derivatives [TPPSMn(OAc)]4-(NH4+)4 and [TArPSMn(OAc)]4-(NH4+)4, where Ar = 4-O-[2-[2-(2-methoxy)ethoxy]eth…

Protonation and Electrochemical Properties of Pyridyl- and Sulfonatophenyl-Substituted Porphyrins in Nonaqueous Media

International audience; The protonation and electrochemical properties of positively charged and negatively charged porphyrins are reported in up to five different nonaqueous solvents. The positively charged porphyrins are represented by mono- and di-pyridyl derivatives having the formula Pyx(PhMe)4-xPM, where P=the dianion of the porphyrin macrocycle, PhMe is a meso-tolyl group, Py a meso-pyridyl group, x=1 or 2, and M=H2, NiII, CuII, ZnII, or CoII. The negatively charged porphyrins are comprised of meso-tetrasulfonato derivatives having the formula [(R)4(TPPS)H2]4−(X+)4, where [(TPPS)H2]4− represents the porphyrin with four SO3− groups on the meso-phenyl substituents of the macrocycle, R=…

Electrochemistry of Bis(pyridine)cobalt (Nitrophenyl)corroles in Nonaqueous Media

International audience; A series of bis(pyridine)cobalt corroles with one or three nitrophenyl groups on the meso positions of the corrole macrocycle were synthesized and characterized as to their electrochemical and spectroscopic properties in dichloromethane, benzonitrile, and pyridine. The potentials for each electrode reaction were measured by cyclic voltammetry and the electron-transfer mechanisms evaluated by analysis of the electrochemical data combined with UV-visible spectra of the neutral, electroreduced, and electroxidized forms of the corroles. The proposed electronic configurations of the initial compounds and the prevailing redox reactions involving the electroactive central c…

Recent developments in dipyrrin based metal complexes: Self-assembled nanoarchitectures and materials applications

While dipyrrin-boron complexes (BODIPYs) and their derivatives have attracted much attention, dipyrrin-based metal complexes recently appeared as a novel luminescent material. So far, dipyrrin-metal complexes have been regarded as non-luminescent or weakly luminescent. Interestingly, introduction of steric hindrance at the meso-position and the development of heteroleptic complexes with proper frontier orbital ordering are two recent strategies that have been developed to improve their luminescent ability. Compared with BODIPYs, one of the distinctive advantages of dipyrrin-metal complexes is that they can form a series of self-assembled supramolecules and polymer assemblies via facile coo…

Cyclotriveratrylene-Containing Porphyrins

International audience; The C-3-symmetric cyclotriveratrylene (CTV) was covalently bonded via click chemistry to 1, 2, 3, and 6 zinc(II) porphyrin units to various host for C-60. The binding constants, Ka, were measured from the quenching of the porphyrin fluorescence by C-60. These constants vary between 400 and 4000 M-1 and are considered weak. Computer modeling demonstrated that the zinc(II) porphyrin units, [Zn], exhibit a strong tendency to occupy the CTV cavity, hence blocking the access for C-60 to land on this site. Instead, the pincer of the type [Zn]-[Zn] and in one case [Zn]-CTV, were found to be the most probable geometry to promote host-guest associations in these systems.

Synthesis and characterization of zinc carboxy–porphyrin complexes for dye sensitized solar cells

Two zinc porphyrins, 2 and 8, have been synthesized. Porphyrin 8 displays better electronic communication between the dye and the TiO2 electrode. Photophysical measurements and electrochemistry experiments suggest that both porphyrins are very promising sensitizers for dye-sensitized solar cells (DSSCs). It was found that their molecular orbital energy levels favor electron injection and dye regeneration in DSSCs. Solar cells sensitized by 2 and 8 were fabricated, and it was found that they show power conversion efficiencies (PCEs) of 5.27% and 7.13%, respectively. Photovoltaic measurements (J–V curves) together with the incident photon-to-electron conversion efficiency spectra of the two c…

SAW based CO2 sensor: influence of functionalizing MOF crystal size on the sensor's selectivity

International audience; The potential impact of indoor air quality on human health has become an increasingly important topic of public health and, thus, has stimulated an interest in hazardous compounds survey such as carbon dioxide. To address this issue, we started the development of a Surface Acoustic Wave device functionalized with metal-organic framework for the selective detection of carbon dioxide. Here, we propose preliminary results on the influence of the size of the metal-organic framework crystals on the sensor’s selectivity and on its evolution with the ageing of the sensor

Synthesis of flexible nanotweezers with various metals and their application in carbon nanotube extraction

Bisporphyrin-based flexible nanotweezers with various metals were synthesized and applied to the extraction of single-walled carbon nanotubes. Homo- and hetero-metallic bisporphyrins containing Co2+ were found to afford higher SWNT-extraction ability, while no or a little amount of SWNTs were extracted by bisporphyrins with other metals.

Electrochemistry of Mono- and Bis-CN Ligated Cobalt Corroles

International audience; The electrochemical properties of numerous transition metal corroles have been examined under a variety of<br&gtsolution condition with special emphasis being placed on the innocent or non-innocent nature of the corrole<br&gtmacrocycle. This property, as well as the half-wave potentials and sites of electron transfers, are known to be<br&gtstrongly influenced by the type of central metal ion and degree of axial coordination, namely 4, 5 or 6-coordinate.<br&gtThe redox potentials of metallocorroles are also dependent upon the solvent and inductive, resonance or steric<br&gteffects dictated by peripheral substituents at the meso or β-pyrrole positions of the corrole li…

Porphyrin Antenna-Enriched BODIPY–Thiophene Copolymer for Efficient Solar Cells

International audience; Low bandgap A−π–D copolymer, P(BdP-DEHT), consisting of alternating BOronDIPYrromethene (BODIPY) and thiophene units bridged by ethynyl linkers, and its porphyrin-enriched analogue, P(BdP/Por-DEHT), were prepared, and their optical and electrochemical properties were studied. P(BdP-DEHT) exhibits strong absorption in the 500–800 nm range with an optical bandgap of 1.74 eV. On the basis of cyclic voltammetry, the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels are evaluated to be −5.40 and −3.66 eV, respectively. After the anchoring of zinc(II) porphyrin on the BODIPY unit, P(BdP/Por-DEHT) displays broadened absor…

Functionnalized Surface Acoustic Wave Sensors for the Detection of Hazardous Gases

International audience; In this work, we show the capabilities of Surface Acoustic Wave (SAW) devices to probe the properties of gas sensitive materials for the manufacturing of hazardous gas sensors. The great capabilities of cobalt corroles for the trapping of carbon monoxide (CO) were exploited to produce selective sensors. These corroles were deposited on SAW delay lines surfaces and then exposed to carbon monoxide (CO) in standard conditions. Concentrations of a few hundreds of ppb were measured emphasizing the interest of such sensors for the detection of CO. Another type of sensitive layers exhibiting specific porosity adapted to the trapping of formaldehyde (CH$_2$O) were deposited …

Mono-DMSO ligated cobalt nitrophenylcorroles: electrochemical and spectral characterization

Four mono-DMSO ligated cobalt corroles with one or three meso-nitrophenyl substituents on the macrocycle were synthesized and investigated as to their electrochemical and spectroscopic properties in CH2Cl2 and DMSO. Comparisons are made between redox reactions of the five-coordinate DMSO adducts in the current study and earlier examined five- and six-coordinate cobalt corroles with pyridine axial ligands which were characterized in a variety of nonaqueous electrochemical solvents. The binding of carbon monoxide (CO) is also investigated.

Synthesis and Characterization of Carbazole-Linked Porphyrin Tweezers

Herein the synthesis, spectroscopic characterization, two-photon absorption and electrochemical properties of 3,6-disubstituted carbazole tweezers is reported. A dimer resulting from a Glaser homocoupling was isolated during a Sonogashira coupling reaction between a diethynyl-carbazole spacer and a 5-bromo-triarylporphyrin and the properties of this original compound were compared with the 3,6-disubstituted carbazole bisporphyrin tweezers. The dyads reported herein present a two-photon absorption maximum at 920 nm with two-photon absorption cross-section in the 1200 GM range. Despite a strong linear absorption in the Soret region and moderate fluorescence quantum yield, they both lead to a …

Disclosing the actual efficiency of G-quadruplex-DNA–disrupting small molecules

AbstractThe quest for small molecules that avidly bind to G-quadruplex-DNA (G4-DNA, or G4), so called G4-ligands, has invigorated the G4 research field from its very inception. Massive efforts have been invested to i- screen or design G4-ligands, ii- evaluate their G4-interacting properties in vitro through a series of now widely accepted and routinely implemented assays, and iii- use them as unique chemical biology tools to interrogate cellular networks that might involve G4s. In sharp contrast, only uncoordinated efforts at developing small molecules aimed at destabilizing G4s have been invested to date, even though it is now recognized that such molecular tools would have tremendous appl…

DNA structure-specific sensitization of a metalloporphyrin leads to an efficient in vitro quadruplex detection molecular tool

International audience; The search for convenient molecular probes for detecting DNA and RNA quadruplexes in vitro is marked by a rapid pace of progress, spurred on by the multiple roles these higher-order nucleic acid structures play in many genetic dysregulations. Here, we contribute to this search, reporting on a palladated porphyrin named Pd.TEGPy: its efficiency as quadruplex-selective fluorescent dye relies on a structural design that endows it with attractive supramolecular and electronic properties and makes it an efficient turn-on, quadruplex-selective fluorescent stain thanks to a DNA-mediated sensitization mechanism that ensures a high level of specificity.

Porous Organic Polymers (POPs) based on cobalt corroles for the detection of carbon monoxide

International audience; Detection of carbon monoxide (CO) at few ppm levels is a critical point for quality control of domestic and<br&gtindustrial environment. CO is responsible for thousands of intoxications and hundreds of deaths per year in the<br&gtworld. Moreover, CO is a residual gas found in the industrial dihydrogen used for Proton Exchange Membrane<br&gtfuel cell, and deactivates the fuel cell prematurely. Corroles have been largely used in sensing applications.[1]<br&gtCobalt corroles display high binding affinity for carbon monoxide even in the presence of nitrogen and<br&gtdioxygen.[2] The affinity of the Co(III) metallocorroles for CO is directly correlated with the Lewis acid…

Ligand Noninnocence in Cobalt Dipyrrin–Bisphenols: Spectroscopic, Electrochemical, and Theoretical Insights Indicating an Emerging Analogy with Corroles

Three cobalt dipyrrin-bisphenol (DPPCo) complexes with different meso-aryl groups (pentafluorophenyl, phenyl, and mesityl) were synthesized and characterized based on their electrochemistry and spectroscopic properties in nonaqueous media. Each DPPCo undergoes multiple oxidations and reductions with the potentials, reversibility, and number of processes depending on the specific solution conditions, the specific macrocyclic substituents, and the type and number of axially coordinated ligands on the central cobalt ion. Theoretical calculations of the compounds with different coordination numbers are given in the current study in order to elucidate the cobalt-ion oxidation state and the innoc…

A3- and A2B-fluorocorroles: synthesis, X-ray characterization and antiviral activity evaluation against human cytomegalovirus infection

Twenty-nine fluorinated corroles were prepared, spectroscopically characterized, and studied for their antiviral activity against human cytomegalovirus infection. Six corroles were also fully characterized by X-ray crystallography giving insights on their geometrical features. The halogenated corroles reported herein exhibit significantly improved antiviral activity over their non-halogenated counterparts and over nitro-corrole analogs previously reported. Full activity of thirteen A3-corroles is achieved with four fluorine atoms present on the meso-phenyl ring reaching a selectivity index above 300. The maximum activity is achieved for A2B-corroles with selectivity indexes above 400. We th…

Porphyrin-Based Design of Bioinspired Multitarget Quadruplex Ligands

Secondary nucleic acid structures, such as DNA and RNA quadruplexes, are potential targets for cancer therapies. Ligands that interact with these targets could thus find application as anticancer agents. Synthetic G-quartets have recently found numerous applications, including use as bioinspired G-quadruplex ligands. Herein, the design, synthesis and preliminary biophysical evaluation of a new prototype multitarget G-quadruplex ligand, (PNA)PorphySQ, are reported, where peptidic nucleic acid guanine ((PNA)G) was incorporated in the porphyrin-templated synthetic G-quartet (PorphySQ). Using fluorescence resonance energy transfer (FRET)-melting experiments, PorphySQ was shown to possess enhanc…

A Very Low Band Gap Diketopyrrolopyrrole-Porphyrin Conjugated Polymer

International audience; A porphyrin-diketopyrrolopyrrole-containing polymer (poly(porphyrin-diketopyrrolopyrrole) (PPDPP)) shows impressive molar absorption coefficients from lambda=300 to 1000 nm. The photophysical and structural properties of PPDPP have been studied. With PPDPP as the electron donor and [ 6,6]phenyl C-71 butyric acid methyl ester (PC71BM) as the electron acceptor, the bulk heterojunction polymer solar cell showed overall power conversion efficiencies of 4.18 and 6.44% for as-cast and two-step annealing processed PPDPP: PC71BM (1: 2) active layers, respectively. These results are quite impressive for porphyrin-containing polymers, especially when directly included in the p…

Influence of interfering gases on a carbon monoxide differential sensor based on SAW devices functionalized with cobalt and copper corroles

International audience; <!--[if gte mso 9]&gt<xml&gt <w:WordDocument&gt <w:View&gtNormal</w:View&gt <w:Zoom&gt0</w:Zoom&gt <w:TrackMoves/&gt <w:TrackFormatting/&gt <w:HyphenationZone&gt21</w:HyphenationZone&gt <w:PunctuationKerning/&gt <w:ValidateAgainstSchemas/&gt <w:SaveIfXMLInvalid&gtfalse</w:SaveIfXMLInvalid&gt <w:IgnoreMixedContent&gtfalse</w:IgnoreMixedContent&gt <w:AlwaysShowPlaceholderText&gtfalse</w:AlwaysShowPlaceholderText&gt <w:DoNotPromoteQF/&gt <w:LidThemeOther&gtFR</w:LidThemeOther&gt <w:Compatibility&gt <w:BreakWrappedTables/&gt <w:SnapToGridInCell/&gt <w:WrapTextWithPunct/&gt <w:UseAsianBreakRules/&gt <w:DontGrowAutofit/&gt <w:SplitPgBreakAndParaMark/&gt <w:EnableOpenTypeKe…

Near-infrared emissive bacteriochlorin-diketopyrrolopyrrole triads: Synthesis and photophysical properties

International audience; The synthesis of unprecedented energy transfer triads containing a near-infrared (NIR) emissive bacteriochlorin subunit and two diketopyrrolopyrrole (DPP) moieties linked to each other via ethynyl or zero-carbon spacers is presented. Their optical and fluorescence properties were determined in CHCl3 and toluene. These photophysical measurements highlight the ability of DPP scaffold to act as an effective energy donor, which once excited in the range 450-550 nm resulting nearly exclusively NIR emission of hydroporphyrin (ETE > 96%). Since DPP dyes are valuable structurally tunable fluorophores that may be used in the construction of high-performance multicomponent pho…

Redox properties of nitrophenylporphyrins and electrosynthesis of nitrophenyl-linked Zn porphyrin dimers or arrays

Five nitrophenylporphyrins were investigated as to their electrochemical properties in CH 2 Cl 2 containing 0.1 M TBAP. The investigated compounds are represented as ( NO 2 Ph )x Ph 4-x PorM , where Por represents the dianion of the porphyrin macrocycle, Ph is a phenyl group on meso-position of the macrocycle, NO 2 Ph is a meso-substituted nitrophenyl group, M = 2 H , Pd II or Zn II and x = 1 or 2. Each porphyrin undergoes an initial one electron reduction at E1/2 = -1.07 to -1.12 V where the added negative charge is almost totally localized on the meso-nitrophenyl group of the compound. This reversible reduction is then followed by one or more irreversible reductions of the nitrophenyl an…

Slow and Fast Singlet Energy Transfers in BODIPY-gallium(III)corrole Dyads Linked by Flexible Chains

Red (no styryl), green (monostyryl), and blue (distyryl) BODIPY-gallium(III) (BODIPY = boron-dipyrromethene) corrole dyads have been prepared in high yields using click chemistry, and their photophysical properties are reported. An original and efficient control of the direction of the singlet energy transfers is reported, going either from BODIPY to the gallium-corrole units or from gallium-corroles to BODIPY, depending upon the nature of the substitution on BODIPY. In one case (green), both directions are possible. The mechanism for the energy transfers is interpreted by means of through-space Förster resonance energy transfer (FRET).

Gold dipyrrin-bisphenolates: A combined experimental and DFT study of metal-ligand interactions

Given that noninnocent and metalloradical-type electronic structures are ubiquitous among dipyrrin-bisphenolate (DPP) complexes, we synthesized the gold(III) derivatives as potentially innocent paradigms against which the properties of other metallo-DPP derivatives can be evaluated. Electronic absorption spectra, electrochemical studies, a single-crystal X-ray structure, and DFT calculations all suggest that the ground states of the new complexes indeed correspond to an innocent AuIII–DPP3−, paralleling a similar description noted for Au corroles. Interestingly, while DFT calculations indicate purely ligand-centered oxidations, reduction of AuDPP is predicted to occur across both the metal …

A3- and A2B-nitrocorroles: synthesis and antiviral activity evaluation against human cytomegalovirus infection

Human cytomegalovirus (hCMV) is responsible for several pathologies impacting immunocompromised patients and can trigger life-threatening infection. Several antivirals are available and are used in the clinic, but hCMV resistant strains have appeared and patients have encountered therapeutic failure. Hence, there is a constant need for new best in class or first in class antiviral molecules. We have previously shown that nitrocorroles could be used as a potent anti-hCMV agent without acute toxicity in mice. They therefore represent an excellent platform to perform structure–activity relationship (SAR) studies and to increase efficiency or reduce toxicity. We have generated original A2B- and…

CCDC 1539258: Experimental Crystal Structure Determination

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CCDC 1578032: Experimental Crystal Structure Determination

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CCDC 1910519: Experimental Crystal Structure Determination

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CCDC 1964008: Experimental Crystal Structure Determination

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CCDC 1880078: Experimental Crystal Structure Determination

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CCDC 1812155: Experimental Crystal Structure Determination

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CCDC 1830060: Experimental Crystal Structure Determination

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CCDC 1554869: Experimental Crystal Structure Determination

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CCDC 1830057: Experimental Crystal Structure Determination

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CCDC 977462: Experimental Crystal Structure Determination

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CCDC 1910517: Experimental Crystal Structure Determination

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CCDC 1910516: Experimental Crystal Structure Determination

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CCDC 1830059: Experimental Crystal Structure Determination

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CCDC 1910518: Experimental Crystal Structure Determination

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CCDC 1910052: Experimental Crystal Structure Determination

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CCDC 1910515: Experimental Crystal Structure Determination

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CCDC 882546: Experimental Crystal Structure Determination

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CCDC 1815709: Experimental Crystal Structure Determination

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CCDC 1910514: Experimental Crystal Structure Determination

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CCDC 1830058: Experimental Crystal Structure Determination

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