Introducing immobilized metal phthalocyanines as spin-injection and detection layers in organic spin-valves: Spin-tunneling and spin-transport regimes

In (organic) spin-valve devices, two ferromagnetic electrodes having different coercive fields are used to achieve an anti-parallel configuration necessary to enforce spin-flip of electrons within the semiconductor spacer layer. Here we report a use of immobilized magnetic organic molecules as spin-injection and spin-detection layers to form pre-fabricated spin-valve devices. While immobilized manganese- and nickel-phthalocyanines were used as spin-injection and spin-detection layers both, copper phthalocyanine acted as the spacer layer in the all-organic spin-valve devices.In the current-voltage characteristics of parallel and anti-parallel configurations, the electrical resistance was always higher for the latter one implying positive magnetoresistance in the material. By lowering thickness of the spacer layer down to a monolayer region, a tunneling regime could be achieved; spin-flip process in organic spin-valves has been found to be facile in the tunneling regime as compared to that during the spin-transport process through a thicker spacer layer.     

New Octopus-like Phthalocyanines as Fullerene Receptors: Synthesis and Photophysical Investigation

Octopus-like zinc and magnesium phthalocyaninates bearing eight flexible benzylated diethylene glycol chains were synthesized and their interaction with fullerenes C₆₀ and C₇₀ was investigated by UV-Vis spectrophotometric titration, as well as by steady-state and time-resolved fluorescence spectroscopy in chloroform and toluene media. These measurements revealed a high affinity of receptors for C₆₀ and C₇₀, with selectivity to C₇₀: binding constants for C₇₀ are almost two times higher than for C₆₀. These results are interpreted by means of quantum-chemical calculations using the PM6-DH2 Hamiltonian. The binding constants also depend on both the nature of the metal ion in the receptor and the solvent. It is expected that the obtained molecules and supramolecular complexes can be used for further elaboration of optoelectronic donor-acceptor materials.     

Electronic states of organic semiconductors vis-à-vis interactions between molecules in a submonolayer through time-restricted electrostatic assembly

We have made in-depth studies to revisit time-restricted layer-by-layer (LbL) electrostatic assembly process of a couple of organic molecules. The studies have been made in relation to electronic states of metal phthalocyanines. We show that by shortening dipping time for adsorption of the active molecules, mass adsorbed in each monolayer can be decreased and hence intermolecular spacing between the molecules can be increased. We have characterized the (sub)monolayers deposited on an electrode with scanning tunneling microscope tip to record tunneling current through the molecules. Results show that the highest occupied molecular orbitals and lowest unoccupied molecular orbitals, and also the difference between the orbitals, that is, the transport gap of the molecules in a (sub)monolayer depends on the dipping time of LbL assembly or molecule-to-molecule separation. We show that interactions between molecules in a monolayer decrease the transport gap of the metal phthalocyanines.     

Tuning the redox properties of Co-N4 macrocyclic complexes for the catalytic electrooxidation of glucose

Graphite electrodes modified with four different cobalt N4 macrocyclics, namely Co tetrapentapyridinophthalocyanine, (CoTPenPyrPc), Co tetrapyridinoporphyrazine (CoTPyPz), Co octa(hydroxyethylthio)phthalocyanine (CoOEHTPc) and Co tetranitrophthalocyanine (CoTNPc) exhibit catalytic activity for the oxidation of glucose in alkaline media. The purpose of this work is to establish correlations between the catalytic activity of these complexes and their redox potential. The activity of the different modified electrodes was tested by linear voltammetry under hydrodynamic conditions using the rotating disk technique. Tafel plots constructed from mass-transport corrected currents give slopes ranging from 0.080 to 0.160 V/decade for the different catalysts which suggests that a first one-electron step is rate controlling with the symmetry of the energy barrier depending on the nature of the ligand of the Co complex. A plot of log I versus the Co(II)/(I) formal potential gives a volcano curve that also includes catalysts studied previously. This illustrates the concept that the formal potential of the catalyst needs to be tuned to a certain value for achieving maximum activity. A theoretical interpretation of these results is given in terms of Langmuir isotherms for the adsorption of glucose on the Co sites of the surface-confined metal complexes.     

Tuning the Stability of Graphene Layers by Phthalocyanine‐Based oPPV Oligomers Towards Photo‐ and Redoxactive Materials

In contrast to pristine zinc phthalocyanine (1), zinc phthalocyanine based oPPV‐oligomers (2–4) of different chain lengths interact tightly and reversibly with graphite, affording stable and finely dispersed suspensions of mono‐ to few‐layer graphene—nanographene (NG)—that are photoactive. The p‐type character of the oPPV backbones and the increasing length of the oPPV backbones facilitate the overall π–π interactions with the graphene layers. In NG/2, NG/3, and NG/4 hybrids, strong electronic coupling between the individual components gives rise to charge transfer from the photoexcited zinc phthalocyanines to NG to form hundreds of picoseconds lived charge transfer states. The resulting features, namely photo‐ and redoxactivity, serve as incentives to construct and to test novel solar cells. Solar cells made out of NG/4 feature stable and repeatable photocurrent generation during several ‘on‐off’ cycles of illumination with monochromatic IPCE values of around 1%.     

Direct observation of the stacked structure in substituted copper phthalocyanine LB films with STM

The in-plane molecular structures of octa-alkyl substituted copper phthalocyanine LB films deposited on graphite have been resolved with a scanning tunnelling microscope (STM). The face-to-face stacking of Pc macrocycles has been observed in the topographies of R₈PcCu monolayers. The stacking period was found to be 3.8–4 Å and the molecular rows were separated by 19 Å and 16 A for (C₆H₁₃)PcCu and (C₅H₁₁)PcCu respectively.     

A Supermolecular Photosensitizer with Excellent Anticancer Performance in Photodynamic Therapy

A supermolecular photosensitizer with excellent anticancer behavior when used for photodynamic therapy (PDT) is fabricated by the incorporation of zinc phthalocyanines (ZnPc) into the gallery of a layered double hydroxide (LDH). The composite material possesses uniform particle size (hydrodynamic diameter ～120 nm), and the host–guest and guest–guest interactions result in a high dispersion of ZnPc in a monomeric state in the interlayer region of the LDH matrix, with high singlet oxygen production efficiency. In vitro tests performed with HepG2 cells reveal a satisfactory PDT effectiveness of the ZnPc(1.5%)/LDH composite photosensitizer: a cellular damage as high as 85.7% is achieved with a rather low dosage of ZnPc (10 μg/mL). An extraordinarily high specific efficacy is demonstrated (31.59 μg^?1 (J/cm²)^?1), which is over 185.5% enhancement compared with the previously reported photosensitizers under similar test conditions. Furthermore, an in vivo study of the ZnPc(1.5%)/LDH demonstrates excellent PDT performance with an ultra‐low dose (0.3 mg/kg) and a low optical fluence rate (54 J/cm²). In addition, the ZnPc/LDH photosensitizer displays high stability, good biocompatibility, and low cytotoxicity, which would guarantee its practical application. Therefore, this work provides a facile approach for design and fabrication of inorganic–organic supermolecular materials with greatly enhanced anticancer behavior.     

Alternative cathodes based on iron phthalocyanine catalysts for mini- or micro-DMFC working at room temperature

Iron phthalocyanine based cathodes were prepared either by dispersion of FePc on carbon or by electropolymerization of aniline in presence of FeTsPc. The macrocycles based cathodes were compared to a classical commercial Pt/C cathode in a standard three-electrode electrochemical cell and under DMFC conditions at room temperature. It was shown that the molecular dispersion of FeTsPc into a PAni film greatly enhances the activity of the macrocycle catalyst towards oxygen reduction reaction (ORR). But, in the same time, the stability under DMFC conditions is drastically decreased compared to the stability obtained with a FePc/C electrode. It was suggested that this instability of the catalytic film was rather due to the release of the FeTsPc from the polymer than to the destruction of the macrocycle active centre. Even if iron phthalocyanine catalysts display total tolerance to methanol when the anode is fed with a 5 M methanol solution, the comparison between a PAni-FeTsPc/C cathode and a Pt/C cathode in DMFC working conditions is in favor of the Pt/C cathode, in term of maximum achieved power density. However, the ratio (platinum atoms per cm²/number of FeTsPc molecules per cm²) is close to 100, which allows to be optimistic for further enhancement of activity of polymer-FeTsPc electrodes. It was suggested that researches to develop new electron conductive polymers stable under oxidative environment and with a high doping capacity could be a direction to use platinum alternative cathode catalysts in DMFC technology.     

Studies of the adsorption of tetrasulfonated phthalocyanines on graphite substrate

The adsorption of iron and cobalt terasulfonated phthalocyanines (TsPcs) on ordinary pyrolytic graphite has been investigated as a function of pH and ionic strength of the adsorption solution as well as the potential. The charge corresponding to the voltammetric redox peaks of adsorbed complexes was used as a measure of the surface concentration. Adsorption of CoTsPc occurs readily from its freshly prepared aqueous solutions and is generally independent of pH. For FeTsPc, however, adsorption does strongly depend on pH. High surface coverage is achieved only from acid solutions rather than from pure water and alkaline solutions. This can be explained in terms of the form(s) of the complexes existing in the solution phase in the presence of air. uv-Visible spectroscopic studies coupled with the addition of CN⁻ to the macrocycle solutions provide evidence that in pure water and alkaline solutions FeTsPc exists predominantly in the μ-oxo form (FeTsPc)₂O, which seems not to favor the adsorption process. No evidence of the μ-oxo complex was found for FeTsPc in acid solutions and CoTsPc in aqueous solutions over the pH range examined (1–13). The adsorption of FeTsPc was at maximum when the potential was held at −0.55 V vs sce in 0.1 M NaOH.     

Synthesis and spectral properties of axially substituted zirconium(IV) and hafnium(IV) water soluble phthalocyanines in solutions

Methods of synthesis of novel water soluble axially substituted Zr(IV) and Hf(IV) phthalocyanines with gallic, 5-sulfosalicyllic, oxalic acids, and methyl ester of gallic acid as axial ligands coordinated to the central atom metal of phthalocyanine are presented. The absorption spectra of complex solutions in various solvents were characterized. The dependence of the spectral red shift from Reichardt’s empirical polarity parameter is described. The deviation from the linearity of Beer–Bouguer–Lambert law was investigated for the range of concentration 5×10⁻⁶ to 10×10⁻⁵ M. Fluorescent properties of axially substituted phthalocyaninato metal complexes in DMSO solutions were investigated.