Synthesis, electrochemical and spectroelectrochemical characterization of novel soluble phthalocyanines bearing chloro and quaternizable bulky substituents on peripheral positions

A new phthalonitrile derivative (2), bearing diethylaminophenoxy - and chloro-substituents at peripheral positions was synthesized in this work. Cyclotetramerization of (2) in hexanol gave the desired metal-free (4) and metallophthalocyanines (5-8). These new phthalocyanines (4-8) were converted into water-soluble quaternized products by the reaction with methyl iodide (9-11). The novel compounds have been characterized by using elemental analysis, UV-Vis, FT-IR, ¹H NMR and MS spectroscopic data. The aggregation behaviors of the phthalocyanine complexes were studied in different solvents and concentrations. Electrochemical and spectroelectrochemical characterization of the complexes were also performed in solution. Cobalt phthalocyanine gives both metal-based and ring-based reduction processes in comparison to the complexes having 2H⁺, Zn²⁺, Ni²⁺ and Cu²⁺ metal center which give only ring-based reduction processes. Electrochemical and spectroelectrochemical measurements exhibit that all complexes oxidatively electro-polymerize on the Pt working electrode during repetitive cyclic voltammetry measurements. An in-situ electrocolorimetric method was applied to investigate the color of the electrogenerated anionic and cationic forms of the complexes for possible electrochromatic applications.     

Electrochemical and spectroelectrochemical characterization of the phthalocyanines with pentafluorobenzyloxy substituents

The solution redox properties and spectroelectrochemical investigation of the novel metal-free, zinc, nickel and cobalt phthalocyanines with tetra-pentafluorobenzyloxy substituents at the periphery were studied using various electrochemical and spectroelectrochemical measurements. Cyclic voltammetry and differential pulse voltammetry studies show that while Ni(II), Zn(II) and free-phthalocyanines give up to two reduction and two oxidation processes having ligand-based diffusion controlled reversible one-electron electron transfer characters, Co(II) phthalocyanine represents one ligand-based oxidation, one metal-based reduction and one ligand-based reduction processes having diffusion controlled reversible one-electron transfer characters. Assignments of the redox couples are also confirmed by spectroelectrochemical measurements. Reduction potentials of all complexes shift to positive potentials due to the electron withdrawing tetra-pentafluorobenzyloxy substituents compared with those of the phthalocyanines bearing phenoxy derivatives. A linear variation of the first reduction and oxidation potentials versus ze/r has been obtained for zinc and nickel phthalocyanines.     

Synthesis and spectroelectrochemistry of new phthalocyanines with ester functionalities

Metal-free (H₂Pc) and metallophthalocyanines (MPc; M: Co, Zn) with four n-pentyl ester of thioglycolic acid groups have been synthesized by the esterification of the corresponding carboxylic acid derivatives with n-pentanol. The novel phthalocyanine compounds were characterized by elemental analyses, mass, FT-IR and UV-Vis spectral data. The aggregation investigations carried out in different concentrations and solvents indicate that ester substituted metal-free and metallo-phthalocyanine compounds have not shown any aggregation behavior in the concentration range of about 10⁻⁵ M. Electrochemical and in-situ spectroelectrochemical measurements give common MPc based redox behaviors which supported the proposed structure of the complexes. While CoPc gives both metal-based and ring-based redox processes, H₂Pc and ZnPc give only ring-based electron transfer processes. In-situ electrocolorimetric method was applied to investigate the color of the electro-generated anionic and cationic forms of the complexes.     

Voltammetric, in-situ spectroelectrochemical and in-situ electrocolorimetric characterization of phthalocyanines

In this work, electrochemical, and in-situ spectroelectrochemical characterization of the metallophthalocyanines bearing tetra-(1,1-(dicarbethoxy)-2-(2-methylbenzyl))-ethyl 3,10,17,24-tetra chloro groups were performed. Voltammetric and in-situ spectroelectrochemical measurements show that while cobalt phthalocyanine complex gives both metal-based and ring-based redox processes, zinc and copper phthalocyanines show only ring-based reduction and oxidation processes. The redox processes are generally diffusion-controlled, reversible and one-electron transfer processes. Differently lead phthalocyanine demetallized during second oxidation reaction while it was stable during reduction processes. An in-situ electrocolorimetric method, based on the 1931 CIE (Commission Internationale de l’Eclairage) system of colorimetry, has been applied to investigate the color of the electro-generated anionic and cationic forms of the complexes for the first time in this study.     

Synthesis, electrochemistry and in situ spectroelectrochemistry of soluble lead phthalocyanines

The synthesis, characterization and voltammetric and spectroelectrochemical properties of newly synthesized lead phthalocyanines bearing tetra-(1,1-(dicarbpenthoxy)-2-(4-biphenyl)-ethyl), tetra-(1,1-(dicarbpenthoxy)-2-(1-naphthyl)-ethyl and tetra-((1,1,2-(tricarbopentoxyethyl)) substituents have been presented in this work for the first time. The characterization of the complexes was made by elemental analysis, ¹H NMR, FT-IR, UV-vis and Maldi-TOF. The solution redox properties and spectroelectrochemical investigation of the complexes are studied using various electrochemical techniques in DCM on a platinum electrode. Cyclic voltammetry and differential pulse voltammetry studies show that the complexes give three one-electron ligand-based reductions and two one-electron oxidation couples having diffusion-controlled mass transfer character. Assignments of the redox couples were confirmed by spectroelectrochemical measurements. Spectroelectrochemical studies reveal that all complexes are demetallized during the spectroelectrochemical measurement under the applied potentials at the first reduction and oxidation potentials of the complexes. Different ring substituents of the complexes affect the easy demetallization processes of the complexes.     

Voltammetric, spectroelectrochemical, and electrocatalytic properties of thiol-derivatized phthalocyanines

Voltammetric and spectroelectrochemical properties and electrocatalytic activities of thiol-derivatized phthalocyanine complexes for hydrogen production have been investigated. Voltammetric and spectroelectrochemical measurements show that while cobalt phthalocyanine complexes (CoPc) present well defined metal-based and ring-based redox processes, all other complexes give only ring-based reduction and oxidation processes. The redox processes are generally diffusion-controlled, reversible and one-electron transferred processes. The complexes bearing tetra(acetoxyethylthio) substituents represents aggregation tendency in DCM solution. Cobalt and nickel phthalocyanines are easily electrodeposited on the GCE working electrode during the repeating cycles of positive potentials. Electrocatalytic activities of electrodeposited complexes indicated that CoPc catalyzed the proton reduction via the electro-reduced [Co^IPc²⁻]¹⁻ and/or [Co^IPc³⁻]²⁻ species depending on the pH of the aqueous solution.     

Synthesis, electrochemical and electrocatalytic behaviour of thiophene-appended cobalt, manganese and zinc phthalocyanine complexes

This work reports on the syntheses of new thiophene tetra substituted cobalt, manganese and zinc phthalocyanine (CoTETPc, (Cl)MnTETPc and ZnTETPc) complexes. The redox processes due to the thiophene substituent on the ring of the metallophthalocyanines (MPcs) were observed, in addition to Pc ring and metal (for Co and Mn complexes) based redox activity. The electrocatalytic activity of the CoTETPc complex adsorbed on glassy carbon electrode (GCE) by drop/dry-thermal annealing was investigated using l-cysteine. The modified electrode was stable to repetitive use without any signs of deactivation by oxidation products and was used to determine l-cysteine at concentrations between 0.0015 and 1 mM in pH 4 aqueous conditions.     

Synthesis and electrochemical properties of benzyl-mercapto and dodecyl-mercapto tetrasubstituted manganese phthalocyanine complexes

Manganese tetrakis (benzyl-mercapto) phthalocyanine (MnTBMPc) and manganese tetrakis (dodecyl-mercapto) phthalocyanine (MnTDMPc) complexes were synthesized and their spectral and electrochemical properties are reported. Cyclic voltammetric data showed three reversible to quasi-reversible and two irreversible redox processes for both complexes. Ring substituents influenced the positions of both oxidation and reduction redox couples. Spectroelectrochemistry confirmed the first two reductions to be due to Mn^IIIPc²⁻/Mn^IIPc²⁻ and Mn^IIPc³⁻/Mn^IIPc²⁻ processes. The first example of a formation of self-assembled monolayers (SAMs) using thiol substituted MnPc complexes is presented, the SAMs were found to show blocking characteristics towards some faradaic reactions.     

Synthesis and electrochemical characterisation of benzylmercapto and dodecylmercapto tetra substituted cobalt, iron, and zinc phthalocyanines complexes

The work reports on cyclic voltammetry (CV), square wave voltammetry and spectroelectrochemistry of the following complexes: tetrakis (benzylmercapto) phthalocyanine complexes of Zn(II) (ZnTBMPc, 4a), Co(II) (CoTBMPc, 5a), and Fe(II) (FeTBMPc 6a); tetrakis (dodecylmercapto) phthalocyanine complexes of Zn(II) (ZnTDMPc, 4b), Co(II) (CoTDMPc, 5b), and Fe(II) (FeTDMPc, 6b). More reversible CV couples were observed for complexes 4a, 5a, and 6a containing thiol phenyl ring substituents. Complexes 4b, 5b, and 6b containing long chain thiol substituents showed less reversible couples. Complexes 6a and 6b showed a relatively large number of redox processes (5 for 6a and 6 for 6b) within the potential window employed in this work. The processes for FePc derivatives (6a) are assigned to Fe^IIIPc⁻¹/Fe^IIIPc⁻², Fe^IIIPc⁻²/Fe^IIPc⁻², Fe^IIPc⁻²/Fe^IPc⁻², Fe^IPc⁻²/Fe^IPc⁻³, and Fe^IPc⁻³/Fe^IPc⁻⁴ and for the CoPc derivative (5a) to Co^IIIPc⁻¹/Co^IIIPc⁻², Co^IIIPc⁻²/Co^IIPc⁻², Co^IIPc⁻²/Co^IPc⁻², and Co^IPc⁻²/Co^IPc⁻³.     

Spectroelectrochemical characterization and controlled potential chronocoulometric demetallation of tetra- and octa-substituted lead phthalocyanines

The solution redox properties and spectroelectrochemical investigation of the novel lead phthalocyanines carrying chloro alkylthio and alkylmalonyl at periphery were studied using various electrochemical techniques in DCM on a platinum electrode. Cyclic voltammetry and differential pulse voltammetry studies show that all of the complexes give up to five ligand-based diffusion controlled one-electron reversible redox couples. Assignments of the redox couples were confirmed by spectroelectrochemical measurements. Spectroelectrochemical studies reveal that lead phthalocyanine complexes are demetallated during the controlled potential chronocoulometry measurement before the first reduction couple of the complexes.     

Synthesis, characterization and electrochemical properties of polybiselenophene

A novel electrically conducting polymer consisting of selenophene moiety, poly(biselenophene) (PBSE) was generated by chemical and electrochemical polymerization. This polymer gave lower bandgap energy (1.9 eV) than pristine polyselenophene (2.0 eV). The electrochemical and optical properties of PBSE was investigated by UV-Vis near infrared spectroscopy and electrochemistry. In situ electrochemical doping studies of PBSE showed the formation of polaron states at 1.4 and 0.8 eV. Through cyclic voltammetry, the polymer oxidation potential (E_pa) and reduction potential (E_pc) for p-doping process for PBSE were observed at 0.93 and 0.86 V, respectively, at a scan rate of 20 mV s⁻¹. Upon chemical doping using chemical reagents such as iodine and ferric chloride, a maximum conductivity of 0.1 S cm⁻¹ was achieved.     

Electrochemical and spectroelectrochemical evidence of dimerization and oligomerization during the polymerization of terthiophenes

Electrochemical oxidation of terthiophenes leads to polymers forming electroactive layers on the electrode surface. Application of spectroelectrochemical methods and special measurement procedure make it possible to show that intermediate products are formed during polymerization. Detailed spectroscopic analyses reveal the presence of terthiophene dimer, trimer and tetramer which allow to propose a mechanism of polymerization process.     

Synthesis, electro-spectroelectrochemical characterization and electrocatalytic behavior towards dioxygen reduction of a new water-soluble cobalt phthalocyanine containing naphthoxy-4-sulfonic acid sodium salt

A new water-soluble cobalt phthalocyanine, 2(3), 9(10), 16(17), 23(24)-tetrakis(4-(1-naphthoxy-4-sulfonic acid sodium salt)) phthalocyaninato cobalt(II) NhtCoPc, where Nht indicates naphthoxy-4-sulfonic acid sodium salt, was synthesized and its electro-spectroelectrochemical and electrocatalytic behavior towards oxygen reduction reaction were investigated in details. The complexation reaction was monitored with the UV-vis spectral changes of NhtH₂Pc in methanol solution. The reaction was completed when the main Q-band was observed in maximum intensity. The electrochemical studies showed that the cobalt complex exhibited two reversible one-electron reductions with the corresponding anodic wave and an irreversible oxidation reaction in DMSO solution. These reduction processes were assigned to Co(2+)Pc(2−)/Co(+)Pc(2−) and Co(+)Pc(2−)/Co(+)Pc(3−) couples, respectively. The well-defined UV-vis spectra of the mono-anionic species [NhtCo(+)Pc(2−)]⁻, di-anionic species [NhtCo(+)Pc(3−)]²⁻, and mono-cationic species [NhtCo(3+)Pc(2−)]⁺, were obtained by the applied potentials (E_app = −0.60, −1.40, and 0.70 V, respectively) in a thin-layer cell. NhtCoPc was incorporated into the conductive polyaniline (PAni) films as a dopant-anion during electropolimerization in acid medium, and thus formed the Pt/PAni-NhtCoPc electrode. This modified electrode was characterized by scanning electron microscopy (SEM), as well. The addition of NhtCoPc to the polymerization solution changes markedly the morphology of the films obtained and increases the redox-activity towards oxygen reduction of the PAni film formed compared to those of Pt/PAni and bare platinum electrodes in the same experimental conditions.     

Electrocatalytic oxygen reduction and hydrogen evolution reactions on phthalocyanine modified electrodes: Electrochemical, in situ spectroelectrochemical, and in situ electrocolorimetric monitoring

This study describes electrochemical, in situ spectroelectrochemical, and in situ electrocolorimetric monitoring of the electrocatalytic reduction of molecular oxygen and hydronium ion on the phthalocyanine-modified electrodes. For this purpose, electrochemical and in situ spectroelectrochemical characterizations of the metallophthalocyanines (MPc) bearing tetrakis-[4-((4′-trifluoromethyl)phenoxy)phenoxy] groups were performed. While CoPc gives both metal-based and ring-based redox processes, H₂Pc, ZnPc and CuPc show only ring-based electron transfer processes. In situ electrocolorimetric method was applied to investigate the color of the electrogenerated anionic and cationic forms of the complexes. The presence of O₂ in the electrolyte system influences both oxygen reduction reaction and the electrochemical and spectral behaviors of the complexes, which indicate electrocatalytic activity of the complexes for the oxygen reduction reaction. Perchloric acid titrations monitored by voltammetry represent possible electrocatalytic activities of the complexes for hydrogen evolution reaction. CoPc and CuPc coated on a glassy carbon electrode decrease the overpotential of the working electrode for H⁺ reduction. The nature of the metal center changes the electrocatalytic activities for hydrogen evolution reaction in aqueous solution. Although CuPc has an inactive metal center, its electrocatalytic activity is recorded more than CoPc for H⁺ reduction in aqueous solution.     

Synthesis, isolation, spectroscopic and electrochemical characterization of some calcium-containing metallofullerenes

A few Ca-containing mono-metallofullerenes, i.e. Ca@C₇₆, Ca@C₈₈, Ca@C₉₀ (I, II), were synthesized by an improved DC arc discharge method and isolated by a multi-stage HPLC method for the first time. These isomer-separated metallofullerenes were characterized by LD-TOF MS and UV-vis-NIR spectrometry. Their HOMO-LUMO band gaps and possible molecular geometries are discussed according to the absorption spectra in this report. In addition, the cyclic and differential pulse voltammetry of Ca@C₇₆ was conducted in MeCN/C₆H₅CH₃ (1:4 v/v). The voltammograms of Ca@C₈₂ (II, III) and Ca@C₈₄ (II) were also recorded. Their electrochemical behaviors are discussed compared with those of corresponding ytterbium metallofullerenes. The features of the Ca metallofullerenes’ electronic structures are also discussed.     

Synthesis and characterization of poly(N-(2-(thiophen-3-yl)methylcarbonyloxyethyl)maleimide) and its spectroelectrochemical properties

A new monomer; N-(2-(thiophen-3-yl)methylcarbonyloxyethyl) maleimide (NMT) was synthesized. The chemical structure of the monomer was characterized by Nuclear Magnetic Resonance (¹H-NMR) and Fourier Transform Infrared (FTIR) Spectroscopy. Electrochemical polymerization of NMT was performed in acetonitrile (AN)/borontrifloride ethylether (BFEE) solvent mixture (1:1, v/v) where tetrabutylammonium tetrafluoroborate (TBAFB) was utilized as the supporting electrolyte. The resulting conducting polymer was characterized by Fourier Transform Infrared (FTIR) Spectroscopy, thermal analyses and Scanning Electron Microscopy (SEM). Electrical conductivity was measured by the four-probe technique. The spectroelectrochemical behavior and switching ability of P(NMT) film were investigated by UV–Vis spectrophotometry. P(NMT) revealed color changes between yellow and blue in the reduced and oxidized states respectively.     

Perylene diimide-appended mixed (phthalocyaninato)(porphyrinato) europium(III) double-decker complex: Synthesis, spectroscopy and electrochemical properties

Treatment of sandwich-type mixed (phthalocyaninato)(porphyrinato) metal complex [HEu^III{Pc(α-3-OC₅H₁₁)₄}{TriBPP(NH₂)}] (3) [Pc(α-3-OC₅H₁₁)₄ = 1,8,15,22-tetrakis(3-pentyloxy)-phthalocyaninate, TriBPP(NH₂) = 5,10,15-tris(4-tert-butylphenyl)-20-(4-aminophenyl)porphyrinate] with N-n-butyl-1,6,7,12-tetra(4-tert-butylphenoxyl)perylene-3,4-dicarboxylate anhydride-9,10-dicarboxylate imide (2) in the presence of imidazole in toluene afforded the novel perylene diimide-appended mixed (phthalocyaninato)(porphyrinato) europium(III) double-decker complex (5). Porphyrin-PDI dyad 4 was also obtained by similar method. The electronic absorption spectroscopic and electrochemical properties of PDI-appended double-decker 5 and the model compounds 2, 3, and 4 were studied, the results indicated that there was no considerable ground-state interaction between the double-decker unit and the PDI unit in 5. The fluorescence measurements revealed that the emission of PDI unit was effectively quenched by the double-decker unit, suggesting remarkable intramolecular interaction in 5 under excited state.     

Synthesis and electrochemical polymerisation of 3′-functionalised terthiophenes: Electrochemical and spectroelectrochemical characterisation

A new terthienyl derivative, 4′-[(2,2′:5′,2″-terthien-3′-yl)methoxy]-2,2′:6′,2″-terpyridine, was synthesised in order to electrogenerate a new conducting polymer as an electrode coating suitable to complex metal ions. The characteristics of the system obtained have been defined through electrochemical and spectroelectrochemical techniques. The physical and chemical properties of 4′-[(2,2′:5′,2″-terthien-3′-yl)methoxy]-2,2′:6′,2″-terpyridine are compared with those of 3′-hydroxymethyl-2,2′:5′,2″-terthiophene, i.e. the corresponding trimer not bearing the terpyridine ligand. Under the same conditions for both monomers, both electrochemical and spectroelectrochemical tests show that 4′-[(2,2′:5′,2″-terthien-3′-yl)methoxy]-2,2′:6′,2″-terpyridine leads to the formation of a narrower molecular weight distribution, with shorter-conjugated polymer chains.     

Enhancement of solubility via esterification: Synthesis and characterization of octakis (ester)-substituted phthalocyanines

Metal-free and metallophthalocyanines (M = Zn, Ni and ClFe) carrying eight hydroxyethylsulfanyl groups at peripheral positions were prepared from 4,5-bis(hydroxyethylsulfanyl)phthalonitrile. The reactivity of the hydroxyethyl groups was demonstrated by esterification of phthalocyanine derivatives with pyridine-4-carboxylic acid and also ferrocenecarboxylic acid in the presence of dicyclohexylcarbodiimide combined with N,N-dimethylaminopyridine or p-toluenesulfonic acid and acetic anhydride. Unlike the parent phthalocyanines, the symmetrically functionalized phthalocyanines with eight ester units were soluble in common organic solvents such as CHCl₃, THF, pyridine and DMF, sparingly soluble in ethanol and acetone and insoluble in water and hexane. The newly synthesized compounds were characterized by elemental analysis, IR, UV–vis, FAB-MS and ¹H NMR spectroscopy.     

Morphology evolution in anodically electrodeposited manganese oxide nanostructures for electrochemical supercapacitor applications—Effect of supersaturation ratio

An in-depth study of morphology-controlled growth of manganese oxide nanostructures from acetate-containing aqueous solutions was carried out. By varying the deposition parameters, including solution composition, pH value, deposition temperature and current density, a series of manganese oxide nanostructures, including continuous coatings with equiaxed and fibrous features, petal- and flower-like morphologies, discrete oxide clusters, columnar structures and interconnected nanosheets, were anodically deposited on Au-coated glass. Detailed results on the morphology, chemistry and crystal structure of the as-deposited manganese oxide nanostructures suggest that the rich morphology of manganese oxide obtained is primarily determined by the influence of supersaturation ratio on reaction kinetics in the aqueous solutions. The electrochemical properties (specific capacitance, rate capacity and electrochemical impedance response) of manganese oxide nanostructures are carefully examined. The experimental results show that manganese oxide electrodes with oriented nanostructures, such as a columnar structure and an interconnected nanosheet architecture, exhibit enhanced electrochemcial performance by improving manganese oxide utilization.