Sodium-Coordinated Polymeric Phthalocyanines as Stable High-Capacity Organic Anodes for Sodium-Ion Batteries

Sodium-ion batteries(SIBs)have attracted considerable interest as an alternative to lithium-ion batteries owing to their similar electrochemical performance and superior long-term cycle stability.Organic materials are regarded as promising anode materials for constructing SIBs with high capacity and good retention.However,utilization of organic materials is rather limited by their low energy density and poor stability at high current densities.To overcome these limitations,we utilized a novel polymeric disodium phthalocyanines(pNaPc)as SIB anodes to provide stable coordination sites for Na ions as well as to enhance the stability at high current density.By varying the linker type during a one-pot cyclization and polymerization process,two pNaPc anodes with O-(O-pNaPc)and S-linkers(S-pNaPc)were prepared,and their structural and electrochemical properties were investigated.The O-pNaPc binds Na ions with a lower binding energy compared with S-pNaPc,which leads to more facile Na-ion coordination/dissociation when engaged as SIB anode.The use of O-pNaPc significantly improves the redox kinetics and cycle stability and allows the fabrication of a full cell against Na_(3)V_(2)(PO_(4))_(2)F_(3)/C cathode,which demonstrates its practical application with high energy density(288 Wh kg^(-1))and high power density(149 W kg^(-1)).

Redox chemistry of N_(4-)Fe^(2+)in iron phthalocyanines for oxygen reduction reaction

A precise understanding of the redox chemistry of Nm-Mn+(like N4-Fe^(2+))systems is essential for fundamental studies and rational design of Nm-Mn+-based electrocatalysts for the oxygen reduction reaction(ORR).Herein,three different iron phthalocyanines(FePcs)adsorbed on carbon nanotubes((NH2)4FePc@CNTs,(t-Bu)4FePc@CNTs,and FePc@CNTs)were evaluated to demonstrate the effect of the electron donating power of the substituents on the Fe^(3+)/Fe^(2+)redox potential of FePc@CNTs and the role of these composites as ORR mediators in alkaline media.The Fe^(3+)/Fe^(2+)redox potential of the FePcs was found to shift towards the cathodic region upon substitution with electron-donating groups.This up-field shift in the eg-orbital leads to a lower overlap between the onset potential of the Fe^(3+)/Fe^(2+)redox couple and that of the ORR,and thus,the ORR activity decreased in the following order based on the substitution of FePc:-H>-t-Bu>-NH2.

Non-peripherally octaalkyl-substituted nickel phthalocyanines used as non-dopant hole transport materials in perovskite solar cells

This report presents two non-perihperally octaalkyl-substituted nickel phthalocyanines(NiPcs),namely,NiEt2Pc and NiPr_(2)Pc,for use as dopant-free hole transport materials in perovskite solar cells(PSCs).The length extension of the alkyl chains from ethyl to propyl significantly tunes the NiPcs’energy levels,thus reducing charge carrier recombination at the perovskite/hole transport layer(HTL)interface and leading to higher open-circuit voltage(VOC)and short-circuit current density(JSC)observed for the NiPr_(2)Pc-based PSC.And higher charge carrier mobility,higher thin film crystallinity,and lower surface roughness of the NiPr_(2)Pc HTL compared with that of the NiEt2Pc one also lead to higher JSC and fill factor(FF)observed for the NiPr_(2)Pc-based device.Consequently,the NiPr_(2)Pc-based PSC exhibits a higher power conversion efficiency(PCE)of 14.07%than that of the NiEt2Pc-based device(8.63%).

Synthesis and Spectroscopic Properties of a Series of New tetra-Substituted Metal Phthalocyanines

A new class of metal phthalocyanines（MPcs） containing four 8-quinolinol（8-QH） derivative moieties were successfully synthesized and characterized by mass spectroscopy, IR, UV-Vis and element analysis, the results of which were consistent with the proposed structures. All of them can dissolve in common organic solvents, such as dichloromethane, chloroform, and acetone. The effect of metal ion on the absorption of Q band was studied with UV-Vis spectra. The fluorescent properties for those complexes were also investigated.

Photoelectrochemical Character of TiO_2 Nanocrystalline Electrodes Sensitized by Aluminum Phthalocyanines Modified with Sulfonate Groups

Particular kinds of TiO2 nanocrystalline electrodes were sensitized by aluminum phthalocyanines modified with sulfonate groups [ Al（OH） PcSm ]. It was found that in the red region, the electrodes show obvious photoelectrical responses. The surface photovoltage spectra and photocurrent action spectra indicate that in the red region, the monomers of aluminum phthalocyanines have a greater influence on the determination of the photoelectrical response of TiO2 electrodes than the dimers. The dye-sensitized solar cells were obtained by using the aluminum phthalocyaninessensitized TiO2 electrodes and Pt electrodes, which have an open circuit photovoltage of 360 mV, a short circuit photocurrent of 39. 4 μA/cm^2 , a fill factor of 0. 54 and a maximum power output of 7.65 μW/cm^2 under a light intensity of 50 mW/cm^2.

P-functionalized carbon nanotubes promote highly stable electrocatalysts based on Fe-phthalocyanines for oxygen reduction: Experimental and computational studies

Iron(Ⅱ) phthalocyanines(FePc) supported on functionalized nanostructured carbon materials have been studied as electrocatalysts for the oxygen reduction reaction(ORR) in an alkaline medium. Herein, two types of carbon nanotubes(CNTs) have been explored as support, Single-Walled Carbon Nanotubes and Herringbone Carbon Nanotubes(SWCNTs and h CNTs, respectively), both electrochemically modified with ortho-aminophenylphosphonic acid(2APPA), which provides phosphate axial coordinating ligands for the immobilization of FePc molecules. All the catalysts were prepared via a facile incipient wetness impregnation method. Comprehensive experimental analysis together with density functional theory(DFT) calculations has demonstrated both the importance of the five-coordinated Fe macrocycles that favor the interaction between the FePc and the carbon support, as well as the effect of the CNT structure in the ORR. FePc axial coordination provides a better dispersion, leading to higher stability and a favorable electron redistribution that also tunes the ORR performance by lowering the stability of the reaction intermediates. Interestingly, such improvement occurs with a very low content of metal(~1 wt% Fe),which is especially remarkable when h CNT support is employed. This work provides a novel strategy for the development of Fe-containing complexes as precious metal-free catalysts towards the ORR.

Tetraalkyl-substituted zinc phthalocyanines used as anode buffer layers for organic light-emitting diodes

Two soluble tetraalkyl-substituted zinc phthalocyanines(ZnPcs)for use as anode buffer layer materials in tris(8-hydroxyquinoline)aluminum(Alq3)-based organic light-emitting diodes(OLEDs)are presented in this work.The holeblocking properties of these Zn Pc layers slowed the hole injection process into the Alq3 emissive layer greatly and thus reduced the production of unstable cationic Alq3(Alq3^+)species.This led to the enhanced brightness and efficiency when compared with the corresponding properties of OLEDs based on the popular poly-(3,4-ethylenedioxythiophene):poly(styrene sulfonate)(PEDOT:PSS)buffer layer.Furthermore,because of the high thermal and chemical stabilities of these Zn Pcs,a nonaqueous film fabrication process was realized together with improved charge balance in the OLEDs and enhanced OLED lifetimes.

Spectroscopic analysis of the interaction between tetra-(p-sulfoazophenyl-4-aminosulfonyl)-substituted aluminum(Ⅲ)phthalocyanines and serum albumins

The binding interaction between tetra-(p-sulfoazophenyl-4-aminosulfonyl)-substituted aluminum(Ⅲ)phthalocyanine(AIPc),and two-serum albumins(bovine serum albumin(BSA)and human serum albumin(HSA))has been investigated.AlPc could quench the intrinsic fuorescence of BSA and HSA through a static quenching process.The primary and secondary binding sites of AlPc on BSA were domainⅠandⅢof BSA.The primary binding site of AIPc on HSA was domainⅠ,and the secondary binding sites of AlPc on HSA were found at domainsⅠandⅡ.Our results suggest that AIPc readily interact with BSA and HSA implying that the amphiphilic substituents AIPc may contribute to their transportation in the blood.

Theoretical Scanning Tunnelling Microscopy Images of Metal (Fe, Co, Ni and Cu) Phthalocyanines

The scanning tunnelling microscopy (STM) images of isolated iron phthalocyanine (FePc), cobalt phthalocyanine (CoPc), nickel phthalocyanine (NiPc) and copper phthalocyanine (CuPc) are simulated theoretically. All the simulated STM images show submolecular structures and reproduce well the features of the experimental images. The results show that there is a strong dependence of the STM images on the ion valence configuration of the metal ion. At the small tip bias voltages of less than 0.5 V, the central metal ions in NiPc and CuPc appear as holes in the molecular images, while they are the highlighted bumps in FePc and CoPc. The simulated images are interpreted by the fact that both FePc and CoPc systems have a significant dz2 character near the Fermi level while the NiPc and CuPc systems do not. Moreover, we predict that the central nickel ion for NiPc appears as a highlighted point when the tip bias voltage is larger than 0.7 V.

Self-Aggregation Enhanced Third-Order Optical Nonlinearities of Aryloxy Substituted Zinc Phthalocyanines

Third-order optical nonlinearities of three aryloxy substituted phthalocyanines are measured by femtosecond forward degenerate four-wave mixing technique at 800 nm.Ultrafast optical responses are observed and the magnitude of the second-order hyperpolarizabilitiesγof the phthalocyanines is measured to be as large as 10?31 esu.Due to the enhancement of J-aggregates,theγvalue of an aryloxy substituted zinc phthalocyanine in chloroform is approximately 2.2 times larger than that of the dye in methanol.Moreover,the morphologies of aryloxy substituted zinc phthalocyanine in chloroform exhibit that the nanowires with a diameter of 50–100 nm are connected to each other to form an indefinite network structure,while no aggregates are detected when the samples are prepared from a solution in the methanol.

Numerical analyses on optical limiting performances of chloroindium phthalocyanines with different substituent positions

Optical limiting properties of two soluble chloroindium phthalocyanines with a- and β-alkoxyl substituents in nanosecond laser field have been studied by solving numerically the coupled singlet-triplet rate equation together with the paraxial wave field equation under the Crank-Nicholson scheme. Both transverse and longitudinal effects of the laser field on photophysical properties of the compounds are considered. Effective transfer time between the ground state and the lowest triplet state is defined in reformulated rate equations to characterize dynamics of singlet-triplet state population transfer. It is found that both phthalocyanines exhibit good nonlinear optical absorption abilities, while the compound with a-substituent shows enhanced optical limiting performance. Our ab-initio calculations reveal that the phthalocyanine with a-substituent has more obvious electron delocalization and lower frontier orbital transfer energies, which are responsible for its preferable photophysical properties.

Synthesis and Characterization of Novel Mesogenic octa-Substituted Phthalocyanines

Synthesis and separation of asymmetrically octa-substituted phthalocyanines （Pcs） derivatives obtained by cyclotetramerization of two different phthalonitriles （Pns） precursors is described. The phthalonitriles were designed to have different polarity to enable successful chromatographic isolation. The side-chains was designed to lie perpendicular to the plane of the macrocycle via ketal link. It was hoped that the obtained materials would exhibit enhanced solubility and less columnar aggregation both in solution and in the solid state. The preparation of the ketal compounds （2,2-didodecyl- 1,3-benzodioxoles ） with was performed according to Cole method in which catechol and the didodecyl ketone were refluxed in toluene solution in the presence of a catalytic amount of p-toluene sulphonic acid （PTSA）. The resultant water was removed by azeotropic distillation using a Dean-Stark trap. 2,2-didodecyl-l,3-benzodioxoles was brominated then cyanated as described in literature to give the desired phthalonitrile. The other phthalonitrile （4,5-bis（1＇,4＇,7＇,10＇-tetraoxaundecyl） phthalonitrile was obtained also as described in literature. The structures of the obtained isomers were confirmed by spectroscopic methods. Optical microscopy and differential scanning calorimetry （DSC） measurements revealed that two of the obtained derivatives display hexagonal and rectangular columnar liquid crystalline phases （Dhd＆Drd） over a wide temperature range.

X-ray Study on the Ring-substituted Phthalocyanines:Crystal Structure of Metal Free 1,4,8,11,15,18,22,25-Octa-butyloxyphthalocyanine

The crystal structure of 1,4,8,11,15,18,22,25-octa-butyloxyphthalocyanine was determined by X-ray diffraction methods. The crystal is of triclinic, space group P 1 with a = 14.0780(3), b = 14.3480(4), c = 17.0090(2) A, α = 72.156(2), β = 86.193(2), r= 73.655(2)°, C64H82N8O8, Mr = 1091.38, Z = 2, V = 3137.5(1) A3, Dc= 1.155 g/cm3, F(000) = 1172, μ(MoKα) = 0.077 mm-1, the final R = 0.0787 and wR = 0.2240 for 5795 observed reflections with I ≥ 2σ(I). The steric congestion between the neighboring butyloxy groups distorts the core of phthalocyanine into a saddle shape conformation. In the crystal lattice, molecules overlap to each other with π-π interaction but the extent of overlap is different along the three axial directions.

Structural Characterizations for Glass Ionomer Cement Doped with Transition Metal Phthalocyanines

Glass and Glass iomomer cement (GICs) based on a specific composition of cerium phosphate glass (40 CeO2-60P2O5) have been prepared. Effect of the doping type at a fixed doping concentration from metal-phthalocyanines (M-PCs) on material structure and morphologies has been carefully studied. The corresponding changes in the material structure were widely followed up by?31P MAS NMR, X-Ray diffraction and FTIR spectroscopy. The network structure of both base glass and GIC which all free from metal phthalocyanines has been confirmed to be amorphous. GIC doped with M-PCs has shown a more ordered structure. There were clear changes in the position and intensities of?31P NMR spectral peaks of glasses upon changing the dopant type. In all cases, a little concentration from M-Phthalocyanine (0.8 mol%) leads to changing the network structure from amorphous to a more ordered structure. Phosphate structural phases are evidenced to be formed upon addition of a fixed amount of M-PCs (Ga, Co, Fe). The morphologies of some selected samples were characterized by SEM. The micrographs have revealed that formulating of cerium phosphate powder of the amorphous glass with a polymeric acid successfully led to the formation of CePO4-H2O bundles phases. But formulation with GIC containing Co or Fe or Ga Phthalocyanine can simply form co-aligned linear slaps and elongated nanofibers which are consisted of hydrated and carbonated CePO4?a GaPO4, FePO4?or CoPO4?crystals. The structure of all doped materials has a lower crack length than that of base glass. This was discussed on bases of formation of more aligned and elongated tough-fibers in matrix of all doped materials. Such tough fibers have ability to withstand breaking stress via suppressing crack propagation.

Interaction of Cationic and Anionic Phthalocyanines with Adenosine Deaminase, Molecular Dynamics Simulation and Docking Studies

Interactions of anionic, cationic and metal phthalocyanine with adenosine deaminase were studied by molecular dynamics and docking simulation. Structural parameters such as solvent accessible surface area (SAS), mid-point of transition temperature (Tm), radial distribution function (RDF) and hydrogen bond, helix, coil, beta percentage and other physical parameters were obtained. The denaturation of adenosine deaminase (ADA) by heat, anionic and cationic phthalocyanines was compared. A series of 20 ns simulation performed at temperatures ranging from 275 to 450 K, starting from the ADA native structure. Results of radial distribution functions (RDFs) showed that metallic derivative at low concentration behaves the same as osmolytes that increases the beta form and increases the enzyme stability. Molecular docking studies have been carried out to confirm the simulation results. Investigation of binding site and free energy confirmed that the efficiency of interaction with adenosine deaminase depends on metal core. Binding energy of non-metallic form is more negative than metallic form and it significantly decreases for phthalocyanine. Self-aggregation of anionic phthalocyanine decreases in comparison with cationic derivative, therefore enzyme denaturation in the presence of anionic form is higher than the other. Furthermore, thermal stability of the enzyme also depends on temperature in presence of phthalocyanine. Binding site of phthalocyanine on the enzyme has been identified by docking analysis.

Nonlinear Refraction of Peripheral-Substituted Zinc Phthalocyanines Investigated by Nanosecond and Picose-cond Z Scans

The singlet and triplet excited-state refraction cross-sections of dimethyl sulfoxide (DMSO) solutions of ten zinc phthalocyanine derivatives with mono-or tetra-peripheral substituents at 532 nm were obtained by simultaneous fitting of closed-aperture Z scans with both nanosecond and picosecond pulse widths. Self-focusing of both nanosecond and picosecond laser pulses was observed in all complexes at 532-nm wavelength. The complexes with tetra-substituents at the ?-position exhibit relatively larger refraction cross-sections than the other complexes. The wavelength dependence of the singlet refraction cross-section of a representative complex was observed to be non-monotonic in the range of 470 - 550 nm.

Design consideration of phthalocyanines as sensitizers for enhanced sono-photodynamic combinatorial therapy of cancer

Cancer remains one of the diseases with the highest incidence and mortality globally.Conventional treatment modalities have demonstrated threatening drawbacks including invasiveness,noncontrollability,and development of resistance for some,including chemotherapy,radiation,and surgery.Sono-photodynamic combinatorial therapy(SPDT)has been developed as an alternative treatment modality which offers a non-invasive and controllable therapeutic approach.SPDT combines the mechanism of action of sonodynamic therapy(SDT),which uses ultrasound,and photodynamic therapy(PDT),which uses light,to activate a sensitizer and initiate cancer eradication.The use of phthalocyanines(Pcs)as sensitizers for SPDT is gaining interest owing to their ability to induce intracellular oxidative stress and initiate toxicity under SDT and PDT.This review discusses some of the structural prerequisites of Pcs which may influence their overall SPDT activities in cancer therapy.

Porphyrins,phthalocyanines,and related covalent-organic frameworks in the photochemical and electrochemical water splitting:A review

In this review,the possibilities of photochemical and electrochemical water splitting(WS)using porphyrins,phthalocyanines,related macrocycles,and their metal complexes are discussed.Significant efforts are being carried out in order to develop novel and cheap methods for water decomposition to generate inexhaustible greener energy sources(molecular hydrogen)instead of oil and gas.The processes of WS in heterogeneous and homogeneous media require novel photo-and electrocatalysts,in particular those on macrocycle basis.A high WS efficiency has been observed for porphyrins and phthalocyanines,showing their suitability both for HER and OER processes are available using these relative compounds for WS purposes.Porphyrins can be used in photocatalytic and electrocatalytic WS processes both in their free forms or as metal porphyrins/porphyrinates,mainly loaded on various inorganic materials,such as Au NPs,C_(3)N_(4),GaP,KTaO_(3),GaP,and so on,as part of porphyrin-containing polymers or on electrode surface as modifying coatings,being sometimes better than commercial catalysts,such as Pt/C.Photocatalytic H2 evolution can be considerably depended on the shape of porphyrin particles;in particular,porphyrin nanowires can yield up to 20 times more H2 than its powder.In certain cases,both HER and OER can be driven in the same electrolyte using metal porphyrins.The capacity of metal porphyrins to generate ROS(in particular,singlet oxygen 1O_(2))under ultrasonic treatment is known and can be successfully used for H_(2)O_(2) and O_(2) generation.Phthalocyanines can be used in similar processes in free form or as composites with inorganic or organic counterparts,being immobilized on nanocarbons,metal oxides and salts,or simply dissolved in water acting in a homogeneous medium.An additional use of ultrasound can lead to better results due to the synergistic effect of the sonochemical treatment and light.Covalent-organic frameworks are also applied for WS purposes and are mainly based on a variety of N-containing ligands,such as triazine,β-ketoenamines,andβ-ketoamines,bipyridine,as well as some S-containing ligands.Metal complexes in WS processes are widely represented by ruthenium coordination compounds,being suitable for future commercial artificial photosynthesis,as well by copper and cobalt coordination compounds with phenantroline,porphyrazine,and related derivatives,being used as electrocatalysts in the form of homogenous molecular films on glassy carbon electrode or as a part of a homogeneous photocatalytic water reduction system for HER processes.The analysis of the photo(electro)catalytic activity of these macrocycles indicated that the Covalent-organic frameworks are highly promising catalysts for H2 evolution from WS.

Electrocatalytic performance of CNTs/graphene composited rare earth phthalocyanines(M=La,Y,Yb,Sc)

In this study,a class of rare earth composite sandwich phthalocyanines(MPcs,M=La,Y,Yb,Sc) were prepared and compounded with graphene and carbon nanotubes to obtain MPc/Gr and MPc/CNTs composites.The electrocatalytic behaviors of MPc/Gr and MPc/CNTs electrodes were further investigated.The results show that the central rare earth metal has a large influence on the electrocatalytic performance.For the MPcs/Gr samples,ScPc with the smallest ionic radius and molecular size can be more uniformly dispersed in graphene,and the hydrogen precipitation overpotential of ScPc/Gr electrode is514 mV,corresponding to a Tafel slope of 148 mV/dec,with better electrocatalytic performance than other rare earth metal phthalocyanines.As for the MPc/CNTs composites,LaPc,which has the largest ionic radius and molecular size,is more uniformly dispersed on the surface of CNTs,so that the LaPc/CNT electrode exhibits the best LSV performance with the smallest corresponding Tafel slope(176 mV/dec).The main reason is the different binding modes of MPcs molecules in Gr and CNTs.When rare earth phthalocyanine is combined with layered graphene,the smallest size of rare earth phthalocyanine(ScPc)is more easily embedded in the graphene layer,resulting in better homogeneity of the composite,larger effective contact area and better electrocatalytic performance.In contrast,when rare earth phthalocyanine is bound to carbon nanotubes in a tubular structure,it is mainly bound by attaching to the surface or being entangled by the carbon nanotubes.In this case,the rare-earth phthalocyanine molecules(LaPc)with larger layer spacing can provide more contact area with CNTs,forming a more uniform and effective composite,which eventually provides more active sites and better electrocatalytic performance.