Octafluoro-Substituted Phthalocyanines of Zinc, Cobalt, and Vanadyl: Single Crystal Structure, Spectral Study and Oriented Thin Films.

In this work, octafluoro-substituted phthalocyanines of zinc, vanadyl, and cobalt (MPcF8, M = Zn(II), Co(II), VO) were synthesized and studied. The structures of single crystals of the obtained phthalocyanines were determined. To visualize and compare intermolecular contacts in MPcF8, an analysis of Hirshfeld surfaces (HS) was performed. MPcF8 nanoscale thickness films were deposited by organic molecular beam deposition technique and their structure and orientation were studied using X-ray diffraction. Comparison of X-ray diffraction patterns of thin films with the calculated diffractograms showed that all three films consisted of a single crystal phase, which corresponded to a phase of single crystals. Only one strong diffraction peak corresponding to the plane (001) was observed on the diffraction pattern of each film, which indicated a strong preferred orientation with the vast majority of crystallites oriented with a (001) crystallographic plane parallel to the substrate surface. The effect of the central metals on the electronic absorption and vibrational spectra of the studied phthalocyanines as well as on the electrical conductivity of their films is also discussed.

Screen-Printed Electrodes Modified with Metal Phthalocyanines: Characterization and Electrocatalysis in Chlorinated Media.

Metal phthalocyanines are well-known sensing phases with applications in different scientific fields due to their interesting properties. Detailed characterization by Raman spectroscopy was performed in order to study the shifting of the vibrational bands related to the coordination sphere of each metal phthalocyanine. In this work, a study involving the use of screen-printed electrodes (SPEs) with various metal phthalocyanines to electrochemically detect and quantify chlorine (Cl2) gas is presented. The Cl2 gas was generated in-situ via oxidation of the chloride present in form of aqueous salt solutions. The developed method offers not only the possibility to quantify chlorine, but also to discriminate among several chlorinated species due to the changes observed in the voltammetric profiles associated with the interaction between the specie assayed and the phthalocyanine metallic center. Optimization of detecting parameters was also performed to apply this procedure for the quantification of chlorine generated from commercial chlorine tablets. The development of this proof of concept shows interesting possibilities and easy-to-use applications with novel on metal phthalocyanines based SPE sensors.

Local aromaticity mapping in the vicinity of planar and nonplanar molecules.

We report on nucleus-independent magnetic shielding (NICS) scans over the centers of six- and five-membered rings in selected metal phthalocyanines (MPc) and fullerene C60 for more accurate characterization of local aromaticity in these compounds. Detailed tests were conducted on model aromatic molecules including benzene, pyrrole, indole, isoindole, and carbazole and subsequently applied to H2 Pc, ZnPc, Al(OH)Pc, and CuPc. Similar behavior of three selected magnetic probes, Bq, 3 He, and 7 Li+ , approaching perpendicularly the ring centers, was observed. For better visualization of shielding zone over the centers of aromatic rings, we introduced a simple mathematical procedure: the first and second derivatives of scan curves with respect to magnetic probe position enabled their additional examination. It allowed an easier localization of curve minimum and discrimination between areas in space varying by the magnetic field magnitude and to illustrate local aromaticity of two different kinds of rings in MPc with better resolution. Our results supported earlier reports on very low aromaticity indexes of pyrrole ring incorporated into MPc and significant aromaticity of the central macrocycle. No direct dependence between harmonic oscillator model of aromaticity and NICS was observed. Instead, a correlation between position of scan curve minimum and its magnitude were observed. In addition, the NICS values and 3 He chemical shifts in the middle of neutral C60 and C606- anion agreed well with the reported experimental NMR values for He@C60 and He@C606- .

Generalized Synthesis of Ultrathin Cobalt-Based Nanosheets from Metallophthalocyanine-Modulated Self-Assemblies for Complementary Water Electrolysis.

The development of effective approaches for preparing large-area, self-standing, ultrathin metal-based nanosheets, which have proved to be favorable for catalytic applications such as water electrolysis, is highly desirable but remains a great challenge. Reported herein is a simple and versatile strategy to synthesize ultrathin Co3 O4 and CoP NSs consisting of close-packed nanoparticles by pyrolyzing cobalt(II) phthalocyanine/graphene oxide (CoPc/GO) assemblies in air and subsequent topotactic phosphidation while preserving the graphene-like morphology. The strong π-π stacking interactions between CoPc and GO, and the inhibiting effect of the tetrapyrrole-derived macrocycle for grain growth during the catalytic carbon gasification contribute to the NSs forming. The resulting homologous Co3 O4 and CoP NSs display outstanding catalytic activity in alkaline media toward the oxygen evolution reaction and the hydrogen evolution reaction, respectively, ascribed to the richly exposed active sites, and the expedited electrolyte/ion transmission path. The integrated asymmetrical two-electrode configuration also presents a superior cell voltage of 1.63 V at 10 mA cm-2 for overall water splitting, accompanied with the excellent durability during long-term cycling. Further evidences validate that this strategy is appropriate to fabricate graphene-like ultrathin NSs of many other metal oxides, such as Fe2 O3 , NiO, MoO3 , and mixed-metal oxides, for various applications.

Fluorinated Metal Phthalocyanines: Interplay between Fluorination Degree, Films Orientation, and Ammonia Sensing Properties.

In this work, the sensor response of MPcFx (M = Cu, Co, Zn; x = 0, 4, 16) films toward gaseous NH3 (10⁻50 ppm) was studied by a chemiresistive method and compared to that of unsubstituted MPc films to reveal the effects of central metals and F-substituents on the sensing properties. A combination of atomic force microscopy and X-ray diffraction techniques have been used to elucidate the structural features of thin MPcFx films deposited by organic molecular beam deposition. It has been shown that the sensor response of MPcF4 films to ammonia is noticeably higher than that of MPc films, which is in good correlation with the values of binding energy between the metal phthalocyanine and NH3 molecules, as calculated by the density functional theory (DFT) method. At the same time, in contrast to the DFT calculations, MPcF16 demonstrated the lesser sensor response compared with MPcF4, which appeared to be connected with the different structure and morphology of their films. The ZnPcF4 films were shown to exhibit a sensitivity to ammonia up to concentrations as low as 0.1 ppm, and can be used for the selective detection of ammonia in the presence of some reducing gases and volatile organic compounds. Moreover, the ZnPcF4 films can be used for the detection of NH3 in the gas mixture simulating exhaled air (N2 76%, O2 16%, H2O 5%, and CO2 3%).

Probing the electronic properties of individual MnPc molecules coupled to topological states.

Hybrid organic/inorganic interfaces have been widely reported to host emergent properties that go beyond those of their single constituents. Coupling molecules to the recently discovered topological insulators, which possess linearly dispersing and spin-momentum-locked Dirac fermions, may offer a promising platform toward new functionalities. Here, we report a scanning tunneling microscopy and spectroscopy study of the prototypical interface between MnPc molecules and a Bi2Te3 surface. MnPc is found to bind stably to the substrate through its central Mn atom. The adsorption process is only accompanied by a minor charge transfer across the interface, resulting in a moderately n-doped Bi2Te3 surface. More remarkably, topological states remain completely unaffected by the presence of the molecules, as evidenced by the absence of scattering patterns around adsorption sites. Interestingly, we show that, while the HOMO and LUMO orbitals closely resemble those of MnPc in the gas phase, a new hybrid state emerges through interaction with the substrate. Our results pave the way toward hybrid organic-topological insulator heterostructures, which may unveil a broad range of exciting and unknown phenomena.

Quantum Spin Exchange Interactions to Accelerate the Redox Kinetics in Li-S Batteries.

Spin-engineering with electrocatalysts have been exploited to suppress the "shuttle effect" in Li-S batteries. Spin selection, spin-dependent electron mobility and spin potentials in activation barriers can be optimized as quantum spin exchange interactions leading to a significant reduction of the electronic repulsions in the orbitals of catalysts. Herein, we anchor the MgPc molecules on fluorinated carbon nanotubes (MgPc@FCNT), which exhibits the single active Mg sites with axial displacement. According to the density functional theory calculations, the electronic spin polarization in MgPc@FCNT not only increases the adsorption energy toward LiPSs intermediates but also facilitates the tunneling process of electron in Li-S batteries. As a result, the MgPc@FCNT provides an initial capacity of 6.1 mAh cm-2 even when the high sulfur loading is 4.5 mg cm-2, and still maintains 5.1 mAh cm-2 after 100 cycles. This work provides a new perspective to extend the main group single-atom catalysts enabling high-performance Li-S batteries.

Transition Metal Phthalocyanines as Redox Mediators in Li-O2 Batteries: A Combined Experimental and Theoretical Study of the Influence of 3d Electrons in Redox Mediation.

Redox mediation is an innovative strategy for ensuring efficient energy harvesting from metal-oxygen systems. This work presents a systematic exploratory analysis of first-row transition-metal phthalocyanines as solution-state redox mediators for lithium-oxygen batteries. Our findings, based on experiment and theory, convincingly demonstrate that d5 (Mn), d7 (Co), and d8 (Ni) configurations function better compared to d6 (Fe) and d9 (Cu) in redox mediation of the discharge step. The d10 configuration (Zn) and non-d analogues (Mg) do not show any redox mediation because of the inability of binding with oxygen. The solution-state discharge product, transition-metal bound Li2O2, undergoes dissociation and oxidation in the charging step of the battery, thus confirming a bifunctional redox mediation. Apart from the reaction pathways predicted based on thermodynamic considerations, density functional theory calculations also reveal interesting effects of electrochemical perturbation on the redox mediation mechanisms and the role of the transition-metal center.

Interface interaction of transition metal phthalocyanines with strontium titanate (100).

We study interface properties of CoPcF x and FePcFx (x = 0 or 16) on niobium-doped SrTiO3(100) surfaces using mainly X-ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy. For all studied molecules, a rather complex, bidirectional charge transfer with the oxide substrate was observed, involving both the macrocycle and the central metal atom. For molecules of the first monolayer, an electron transfer to the central metal atom is concluded from transition metal 2p core level photoemission spectra. The number of interacting molecules in the first monolayer on the oxide surface depends on the central metal atom of the phthalocyanine, whereas the substrate preparation has minor influence on the interaction between CoPc and SrTiO3(100). Differences of the interaction mechanism to related TiO2 surfaces are discussed.

Bifunctional Oxygen Electrocatalysis on Mixed Metal Phthalocyanine-Modified Carbon Nanotubes Prepared via Pyrolysis.

Non-precious-metal catalysts are promising alternatives for Pt-based cathode materials in low-temperature fuel cells, which is of great environmental importance. Here, we have investigated the bifunctional electrocatalytic activity toward the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) of mixed metal (FeNi; FeMn; FeCo) phthalocyanine-modified multiwalled carbon nanotubes (MWCNTs) prepared by a simple pyrolysis method. Among the bimetallic catalysts containing nitrogen derived from corresponding metal phthalocyanines, we report the excellent ORR activity of FeCoN-MWCNT and FeMnN-MWCNT catalysts with the ORR onset potential of 0.93 V and FeNiN-MWCNT catalyst for the OER having EOER = 1.58 V at 10 mA cm-2. The surface morphology, structure, and elemental composition of the prepared catalysts were examined with scanning electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The FeCoN-MWCNT and FeMnN-MWCNT catalysts were prepared as cathodes and tested in anion-exchange membrane fuel cells (AEMFCs). Both catalysts displayed remarkable AEMFC performance with a peak power density as high as 692 mW cm-2 for FeCoN-MWCNT.

Structure and electrochemical properties of carbon nanostructures derived from nickel(II) and iron(II) phthalocyanines.

Mesoporous carbons containing up to 3.6 at.% N and 4.4 at.% O and exhibiting graphitic character have been prepared from Ni(II) and Fe(II) phthalocyanines by direct pyrolysis or by HTC + pyrolysis, and subsequently applied as supercapacitor materials. No mesoporous templates or doping post-treatments were used, and the catalytic effect of Ni(II) and Fe(II), naturally present in the precursor molecules, allowed obtaining graphitic carbons at temperatures ≤ 900 °C. Metals were encapsulated in the core of onion-like structures with no contact with the electrolyte, so that electrodes were prevented from degradation during device operation. The materials exhibited high rate capabilities up to 1 V s-1, higher interfacial capacitances than a wide variety of materials possessing higher surface areas, and high capacitance retentions up to 99% at 5 A g-1 current density throughout 10 000 charge-discharge cycles. The electrochemical performances of the phthalocyanine-derived carbons are due to their graphitic character and to the pseudocapacitance contribution of the surface groups through Faradaic reactions. This work opens a new way to obtain carbon materials from a great family of metal phthalocyanines, since the central metal and the radicals of the latter can be varied to tune the carbon properties for specific applications.

Manipulation of Molecular Spin State on Surfaces Studied by Scanning Tunneling Microscopy.

The adsorbed magnetic molecules with tunable spin states have drawn wide attention for their immense potential in the emerging fields of molecular spintronics and quantum computing. One of the key issues toward their application is the efficient controlling of their spin state. This review briefly summarizes the recent progress in the field of molecular spin state manipulation on surfaces. We focus on the molecular spins originated from the unpaired electrons of which the Kondo effect and spin excitation can be detected by scanning tunneling microscopy and spectroscopy (STM and STS). Studies of the molecular spin-carriers in three categories are overviewed, i.e., the ones solely composed of main group elements, the ones comprising 3d-metals, and the ones comprising 4f-metals. Several frequently used strategies for tuning molecular spin state are exemplified, including chemical reactions, reversible atomic/molecular chemisorption, and STM-tip manipulations. The summary of the successful case studies of molecular spin state manipulation may not only facilitate the fundamental understanding of molecular magnetism and spintronics but also inspire the design of the molecule-based spintronic devices and materials.

Dianionic Titanyl and Vanadyl (Cation+ )2 [MIV O(Pc4- )]2- Phthalocyanine Salts Containing Pc4- Macrocycles.

In this study, the titanyl and vanadyl phthalocyanine (Pc) salts (Bu4 N+ )2 [MIV O(Pc4- )]2- (M=Ti, V) and (Bu3 MeP+ )2 [MIV O(Pc4- )]2- (M=Ti, V) with [MIV O(Pc4- )]2- dianions were synthesized and characterized. Reduction of MIV O(Pc2- ) carried out with an excess of sodium fluorenone ketyl in the presence of Bu4 N+ or Bu3 MeP+ is exclusive to the phthalocyanine centers, forming Pc4- species. During reduction, the metal +4 charge did not change, implying that Pc is an non-innocent ligand. The Pc negative charge increase caused the C-N(pyr) bonds to elongate and the C-N(imine) bonds to alternate, thus increasing the distortion of Pc. Jahn-Teller effects are significant in the [eg(π*)]2 dianion ground state and can additionally distort the Pc macrocycles. Blueshifts of the Soret and Q-bands were observed in the UV/Vis/NIR when MIV O(Pc2- ) was reduced to [MIV O(Pc.3- )].- and [MIV O(Pc4- )]2- . From magnetic measurements, [TiIV O(Pc4- )]2- was found to be diamagnetic and (Bu4 N+ )2 [VIV O(Pc4- )]2- and (Bu3 MeP+ )2 [VIV O(Pc4- )]2- were found to have magnetic moments of 1.72-1.78 µB corresponding to an S=1/2 spin state owing to VIV electron spin. As a result, two latter salts show EPR signals with VIV hyperfine coupling.

Molecular Crystal Engineering: Tuning Organic Semiconductor from p-type to n-type by Adjusting Their Substitutional Symmetry.

Focusing on the bottleneck of molecularly engineered organic semiconductors, a breakthrough is made to tune the electronic properties of organic semiconductors from p-type to n-type by using fluorinated metal phthalocyanines as examples. The experimentally observed p-type to n-type transition characteristics of single-crystal field-effect devices result from a combination of extrinsic and intrinsic properties of materials with different fluoridation substitution.

Single-Molecule Imaging of Iron-Phthalocyanine-Catalyzed Oxygen Reduction Reaction by in Situ Scanning Tunneling Microscopy.

We report herein an in situ electrochemical scanning tunneling microscopy (ECSTM) investigation of iron-phthalocyanine (FePc)-catalyzed oxygen reduction reaction (ORR). A highly ordered FePc adlayer is revealed on a Au(111) electrode. The center ions in the FePc adlayer show uniform high contrast in an oxygen-saturated electrolyte, which is attributed to the formation of an FePc-O2 complex. In situ STM results reveal the sharp contrast change upon shifting the electrode potential to trigger the ORR. Theoretical simulation has supplied further evidence for the contrast difference of the adsorbed FePc species.