Academic literature on the topic 'Fully fluorinated organic sensitizers'

Two newly halogenated chalcones, derivatives of C15H10ClFO (CH-ClF) and C15H10F2O (CH-FF), were synthesized using the Claisen–Schmidt condensation method. Both compounds were crystallized using a slow evaporation method, forming a monoclinic crystal system with a space group of P21 and P21/c, respectively. The compounds were further analyzed using spectroscopic techniques such as Fourier Transform Infrared (FTIR), Nuclear Magnetic Resonance (NMR), and Ultraviolet–Visible (UV–vis) analyses. The single crystal X-ray diffraction method revealed the existence of C−H⋯O and C−H⋯F intermolecular interactions in CH-FF. Hirshfeld surface analysis was performed to confirm the existence of intermolecular interactions in the compounds. The molecular geometries obtained from the X-ray structure determination were further used to optimize the structures using density functional theory (DFT), with the B3LYP/6-311G++(d,p) basis set in the ground state. The TD-DFT/B3LYP method was used to obtain the electronic properties and the HOMO–LUMO energy gap. Both compounds exhibited A-π-A architecture with different halogen substituents in which the CH-FF, containing -fluoro substituents, possessed good electron injection ability due to its electronegative properties. This increased the flow of the charge transfer for the dye regeneration process and enhanced the efficiency of the dye-sensitized solar cell (DSSC).

We describe in this paper that using secondary OH as the kinetic resolution auxiliary group, a series of previously unavailable fluorinated fully-substituted carbon molecules can be obtained with excellent level of enantioselectivities.

Radiation and photodynamic therapies are used for cancer treatment by targeting DNA. However, efficiency is limited due to physico-chemical processes and the insensitivity of native nucleobases to damage. Thus, incorporation of radio- and photosensitizers into these therapies should increase both efficacy and the yield of DNA damage. To date, studies of sensitization processes have been performed on simple model systems, e.g., buffered solutions of dsDNA or sensitizers alone. To fully understand the sensitization processes and to be able to develop new efficient sensitizers in the future, well established model systems are necessary. In the cell environment, DNA tightly interacts with proteins and incorporating this interaction is necessary to fully understand the DNA sensitization process. In this work, we used dsDNA/protein complexes labeled with photo- and radiosensitizers and investigated degradation pathways using LC-MS and HPLC after X-ray or UV radiation.

Nine new fluorinated analogues were synthesised by late-stage functionalisation using Diversinate™ chemistry on the Open Source Malaria (OSM) triazolopyrazine scaffold (Series 4). The structures of all analogues were fully characterised by NMR, UV and MS data analysis; three triazolopyrazines were confirmed by X-ray crystal structure analysis. The inhibitory activity of all compounds against the growth of the malaria parasite Plasmodium falciparum (3D7 and Dd2 strains) and the cytotoxicity against a human embryonic kidney (HEK293) cell line were tested. Some of the compounds demonstrated moderate antimalarial activity with IC50 values ranging from 0.2 to >80 µM; none of the compounds displayed any cytotoxicity against HEK293 cells at 80 µM. Antimalarial activity was significantly reduced when C-8 of the triazolopyrazine scaffold was substituted with CF3 and CF2H moieties, whereas incorporation of a CF2Me group at the same position completely abolished antiplasmodial effects.

AbstractWhile metal-organic frameworks based on aromatic carboxylates are very numerous and well investigated, the chemistry of their fully fluorinated analogues is at the very beginning. This minireview aims at summarizing all metal complexes with octafluorobiphenyl-4,4′-dicarboxylate (oFBPDC2−) anion and in particular, porous coordination polymers, their syntheses, crystal structures and functional properties highlighting the importance of further investigation of such systems.

A solvent-free two-step synthesis of polyfunctionalized pyrazoles under ball-milling mechanochemical conditions was developed. The protocol comprises (3 + 2)-cycloaddition of in situ generated nitrile imines and chalcones, followed by oxidation of the initially formed 5-acylpyrazolines with activated MnO2. The second step proceeds via an exclusive deacylative pathway, to give a series of 1,4-diarylpyrazoles functionalized with a fluorinated (CF3) or non-fluorinated (Ph, COOEt, Ac) substituent at C(3) of the heterocyclic ring. In contrast, MnO2-mediated oxidation of a model isomeric 4-acylpyrazoline proceeded with low chemoselectivity, leading to fully substituted pyrazole as a major product formed via dehydrogenative aromatization. The presented approach extends the scope of the known methods carried out in organic solvents and enables the preparation of polyfunctionalized pyrazoles, which are of general interest in medicine and material sciences.

The use of binary blends of hydrogenated and fluorinated alkanethiolates represents an interesting approach to the construction of anisotropic hybrid organic–inorganic nanoparticles since the fluorinated and hydrogenated components are expected to self-sort on the nanoparticle surface because of their reciprocal phobicity. These mixed monolayers are therefore strongly non-ideal binary systems. The synthetic routes we explored to achieve mixed monolayer gold nanoparticles displaying hydrogenated and fluorinated ligands clearly show that the final monolayer composition is a non-linear function of the initial reaction mixture. Our data suggest that, under certain geometrical constraints, nucleation and growth of fluorinated domains could be the initial event in the formation of these mixed monolayers. The onset of domain formation depends on the structure of the fluorinated and hydrogenated species. The solubility of the mixed monolayer nanoparticles displayed a marked discontinuity as a function of the monolayer composition. When the fluorinated component content is small, the nanoparticle systems are fully soluble in chloroform, at intermediate content the nanoparticles become soluble in hexane and eventually they become soluble in fluorinated solvents only. The ranges of monolayer compositions in which the solubility transitions are observed depend on the nature of the thiols composing the monolayer.

A series of new, fluorinated poly(ester-imides)s has been synthesized by solution condensation, in a high-boiling-point solvent, of dihydroxy compounds containing imide and hexafluoroisopropylidene units with diacid chlorides containing preformed ester groups. Solutions of these polymers in NMP or in a mixture of trifluoroacetic acid with chloroform were cast into colourless, thin, flexible films having a low dielectric constant. These polymers show high thermal stability, with the initial decomposition temperature being over 400cC. The glass transition temperature is in the range 215-272C for fully aromatic structures and is about 170 TC for those polymers containing some ethylene groups along with aromatic ones. All these characteristics are discussed and compared with those of related poly(esterimide)s which do not contain 6F groups.

With the increasing demand for reliable and efficient devices with minimal environmental impact, novel organic materials gain extreme interest in the research community and industry. In this work we present synthetic strategies towards new organic compounds as promising materials for dye sensitized solar cells (DSCs) and low-cost integrated optics along with the investigation of these materials in devices. Despite the recent hype in the research community around DSCs, increasing efficiency of DSCs is still a challenge. In principle, one promising way to obtain DSCs with significantly enhanced efficiency lies in connecting an n-type photoelectrode (i.e. n-Dye/TiO2) with a p-type one (i.e. p-Dye/NiO) leading to a tandem cell composed by two serially connected photoactive electrodes, each contributing with its own photovoltage to the total photovoltage delivered by the cell. Applying such concept could theoretically lead to organic photovoltaic devices with up to 40% overall conversion yield. One of the main limitations in p-type systems, commonly based on NiO, arises from fast charge recombination between the photoinjected hole in NiO, and the reduced dye. Therefore it is crucially important to develop p-type chromophores which could produce a long-lived charge separated state and minimize back recombination. We were thus triggered to explore new organic structures for potentially efficient chromophores for p-type devices, by considering that the intramolecular charge transfer, at the basis of efficient charge separation in donor-acceptor dyes, is strongly dependent on the electron-withdrawing ability of the acceptor. Herein we present charge separators based on organic push-pull systems of tryphenylamine donors and branched electron acceptors (SK2-3-4) based either on Dalton (SK2) or benzothidaziole acceptor groups (SK3-4) which were synthesized and characterized by steady state spectroscopic, electrochemical and computational means. All the dyes exhibit strong charge transfer bands in the visible regions with ground and excited state energetics which are favourable to the sensitization of NiO electrodes. The computational investigation revealed a clear directionality of the lowest excited state exhibiting a marked charge transfer character, shifting the electron density to the acceptor branches, an electronic situation which is favourable to the hole injection in p-type semiconductors. When tested in p-type DSCs the SK series was found capable to sensitize NiO electrodes. The charge recombination kinetics, probed by considering the charge transfer resistance at the NiO/electrolyte interface at a comparable chemical capacitance, showed that the dyes behaved similarly and that the higher Voc observed with the SK4 dye is ostensibly due to a positive shift of the valence band edge, consistent with the shift in the anodic current threshold observed in dark conditions. The second part of this work is dedicated to synthesis and characterisation of metallo-organic materials for optoelectronic devices. Optical amplification plays crucial role in the transmission and manipulation of optical signals in modern telecomunications. Nowadays amplifiers, which rely on erbium ions in a glass matrix, suffer from difficulties in fabrication and the need of high pump power densities to produce gain. Here we show a newly synthesised series of organic fully halogenated optical amplifier materials. We will compare the ability of materials with different halogen atoms in complexes with transition metals to provide population of triplets which together with the lack of CH or OH oscillators in the molecule, can be potentially used as an efficient chromophore to sensitise the erbium ions in a long-lifetime erbium complex. Finally by doping Er(FTPIP)3 with newly designed Zn and Co complexes, we aim to find differences in the lifetime emission from erbium at the important telecommunication wavelength of 1.5 μm.

The quality of human life depends to a large degree on the availability of energy. In recent years, photovoltaic technology has been growing extraordinarily as a suitable source of energy, as a consequence of the increasing concern over the impact of fossil fuels on climate change. Developing affordable and highly efficiently photovoltaic technologies is the ultimate goal in this direction. Dye-sensitized solar cells (DSSCs) offer an efficient and easily implementing technology for future energy supply. Compared to conventional silicon solar cells, they provide comparable power conversion efficiency at low material and manufacturing costs. In addition, DSSCs are able to harvest low-intensity light in diffuse illumination conditions and then represent one of the most promising alternatives to the traditional photovoltaic technology, even more when trying to move towards flexible and transparent portable devices. Among these, considering the increasing demand of modern electronics for small, portable and wearable integrated optoelectronic devices, Fibre Dye-Sensitized Solar Cells (FDSSCs) have gained increasing interest as suitable energy provision systems for the development of the next-generation of smart products, namely “electronic textiles” or “e-textiles”. In this thesis, several key parameters towards the optimization of FDSSCs based on inexpensive and abundant TiO2 as photoanode and a new innovative fully organic sensitizer were studied. In particular, the effect of various FDSSCs components on the device properties pertaining to the cell architecture in terms of photoanode oxide layer thickness, electrolytic system, cell length and electrodes substrates were examined. The photovoltaic performances of the as obtained FDSSCs were fully characterized. Finally, the metal part of the devices (wire substrate) was substituted with substrates suitable for the textile industry as a fundamental step towards commercial exploitation.

Organic compounds of various kinds have been used in the nuclear industry for numerous duties in uranium chemical, metal and ceramic processing plants. In the course of the various operations undertaken, these organic compounds have become contaminated with uranic material, either accidentally or as an inevitable part of the process. Typically, the chemical/physical form and/or concentration of the uranic content of the organics has prevented disposal. In order to address the issue of contaminated liquid organic wastes, the National Nuclear Laboratory (NNL) has developed a suite of treatments designed to recover uranium and to render the waste suitable for disposal. The developed processes are operated at industrial scale via the NNL Preston Laboratory Residue Processing Plant. The Oil Waste Leaching (OWL) Process is a fully industrialised process used for the treatment of contaminated oils with approximately 200 tonnes of uranium contaminated oil being treated to date. The process was originally developed for the treatment of contaminated tributyl phosphate and odourless kerosene which had been adsorbed onto sawdust. However, over the years, the OWL process has been refined for a range of oils including “water emulsifiable” cutting oils, lubricating oils, hydraulic oils/fluids and “Fomblin” (fully fluorinated) oils. Chemically, the OWL process has proved capable of treating solvents as well as oils but the highly volatile/flammable nature of many solvents has required additional precautions compared with those required for oil treatment. These additional precautions led to the development of the Solvent Treatment Advanced Rig (STAR), an installation operated under an inert atmosphere. STAR is a small “module” (100 dm3 volume) which allows the treatment of both water miscible and immiscible solvents. This paper discusses the challenges associated with the treatment of liquid organic wastes and the process developments which have allowed a wide range of materials to be successfully treated.