Synthesis and electrochemical and in situ spectroelectrochemical characterization of manganese, vanadyl, and cobalt phthalocyanines with 2-naphthoxy substituents

Metallo (Mn, Co, VO) phthalocyanines bearing peripheral 2-naphthoxy groups were synthesized by cyclotetramerisation of the corresponding phthalonitrile derivative. The phthalocyanine compounds were characterized by elemental analyses, mass, FT-IR and UV–vis spectral data. Three intense bands in the electronic spectra clearly indicate the absorptions resulting from naphthyl groups along with the Q and B bands of the phthalocyanines. Electrochemical and spectroelectrochemical measurements exhibit that incorporation of redox active metal ions, Co^II and Mn^III, into the phthalocyanine core extends the redox capabilities of the Pc ring including the metal-based reduction and oxidation couples of the metal. Presence of molecular oxygen in the electrolyte system affects the voltammetric and spectroelectrochemical responses of the cobalt and manganese phthalocyanines due to the interaction between the complexes and molecular oxygen. Interaction reaction of oxygen with CoPc occurs via an “inner sphere” chemical catalysis process. While CoPc gives the intermediates [O₂⁻–Co^IIPc⁻²]⁻ and [O₂²–Co^IIPc⁻²]²⁻, MnPc forms μ-oxo MnPc species. An in situ electrocolorimetric method has been applied to investigate the color of the electro-generated anionic and cationic forms of the complexes for possible electrochromatic applications.     

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.     

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.     

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 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.     

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, characterization, electrochemistry and spectroelectrochemistry of novel soluble porphyrazines bearing unsaturated functional groups

Metalloporphyrazines with a 2-methyl-2-pentenyl group fused to each pyrrole unit were synthesized starting with the corresponding unsaturated dicarbonitrile derivative. The new compounds were characterized by elemental analysis together with FTIR, ¹H-NMR, and UV-Vis spectroscopy and via voltammetric and spectrochemical methods. Electrochemical and spectroelectrochemical measurements demonstrate that while metal-free and magnesium porphyrazines gave common porphyrazine (Pz) ring-based electron-transfer reactions, incorporating redox active metal center, Co^II, into the porphyrazine core extended the redox activity of the ring system with reversible metal-based reduction and oxidation couples of the metal center in addition to the common Pz ring-based electron transfer processes. The unsaturated functional groups of the porphyrazines did not alter the common electrochemical behavior of the complexes. An in situ electrocolorimetric method, based on the 1931 CIE (Commission Internationale de l’Eclairage) system of colorimetry, was applied to investigate the color of the electro-generated anionic and cationic forms of the complexes for possible electrochromatic applications.     

Electrochemical characterisation of tetra- and octa-substituted oxo(phthalocyaninato)titanium(IV) complexes

The synthesis and electrochemical characterisation of the following oxotitanium tetra-substituted phthalocyanines are reported: 1,(4)-(tetrabenzyloxyphthalocyaninato)titanium(IV) oxide (5a); 1,(4)-{tetrakis[4-(benzyloxy)phenoxy]phthalocyaninato}titanium(IV) oxide (5b); 2,(3)-(tetrabenzyloxyphthalocyaninato)titanium(IV) oxide (6a) and 2,(3)-{tetrakis[4-(benzyloxy)phenoxy]phthalocyaninato}titanium(IV) oxide (6b). The electrochemical characterisation of complexes octa-substituted with 4-(benzyloxy)phenoxy (9b), phenoxy (9c) and tert-butylphenoxy (9d) groups is also reported. The cyclic voltammograms of the complexes exhibit reversible couples I-III and couple IV is quasi-reversible for complexes 5a, 5b, 6a and 6b. The first two reductions are metal-based processes, confirmed by spectroelectrochemistry to be due to Ti^IVPc²⁻/Ti^IIIPc²⁻ and Ti^IIIPc²⁻/Ti^IIPc²⁻ redox processes and the last two reductions are ring-based processes due to Ti^IIPc²⁻/Ti^IIPc³⁻ and Ti^IIPc³⁻/Ti^IIPc⁴⁻. Chronocoulometry confirmed a one-electron transfer at each reduction step. The electrochemistry of the above complexes is also compared to the previously reported 5c, 5d, 6c and 6d.     

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.     

The synthesis,cyclic voltammetry and spectroelectrochemical studies of Co(II) phthalocyanines tetra-substituted at the α and β positions with phenylthio groups

Non-peripherally substituted cobalt 1,(4)-(tetraphenylthiophthalocyaninato) and peripherally substituted cobalt 2,(3)-(tetraphenylthiophthalocyaninato) complexes were synthesized. Redox processes were observed at E_1/2 = ?1.44 V (I), ?0.39 V (II), +0.37 V (III), +0.78 V (IV) and 1.15 V (V) for the non-peripherally substituted and at E_1/2 = ?1.42 V (I), ?0.57, ?0.39 V (II), +0.27 V (III), +0.79 V (IV) and +1.10 V (V) for the peripherally substituted complexes, respectively. The couples were assigned to Co^IPc^?2/Co^IPc^?3 (I), Co^IIPc^?2/Co^IPc^?2 (II), Co^IIIPc^?2/Co^IIPc^?2 (III), and Co^IIIPc^?1/Co^IIIPc^?2 (IV) using spectroelectrochemistry. The last process (V) could not be ascertained by spectroelectrochemistry but is associated with ring oxidation. Upon reduction or oxidation, the Q band of the non-peripherally substituted complex became less red shifted compared to that of its peripherally substituted counterpart.     

Electrooxidation of hydrazine catalyzed by noncovalently functionalized single-walled carbon nanotubes with CoPc

We report on the electrooxidation of hydrazine catalyzed by single-walled carbon nanotube (SWCNT) functionalized with cobalt phthalocyanine (CoPc) which shows that the presence of the single-walled carbon nanotubes enhances the catalytic activity of the CoPc itself without any change in the reaction mechanism. A synergistic effect, in terms of reactivity when the new nanocomposite material was adsorbed on the GC electrode, was observed. The obtained hybrid electrodes were tested under hydrodynamic conditions, showing two different oxidation processes, which suggest the presence of two different types of active sites on the electrode surface catalyzing the reaction. Electrochemical impedance spectroscopy (EIS) analyses in the presence of [Fe(CN)₆]^3−/4− as a redox probe revealed that the GC/SWCNT + CoPc showed much lower electron-resistance (R_et) confirming the synergistic effect of the composite mentioned above. Atomic force microscopy (AFM) images showed the clear differences in surface roughness for each film, confirming the different compositions of the hybrid electrodes used in this study.     

Characterization of polymeric film of a new manganese phthalocyanine complex octa-substituted with 2-diethylaminoethanethiol, and its use for the electrochemical detection of bentazon

Manganese acetate octakis-(2-diethyaminoethanethiol) phthalocyanine (AcMnODEAETPc) was newly synthesized and characterized by spectroscopic and electrochemical methods. Solution electrochemistry of the complex showed three redox processes assigned to Mn^IIIPc⁻¹/Mn^IIIPc⁻², Mn^IIIPc⁻²/Mn^IIPc⁻² and Mn^IIPc⁻²/Mn^IIPc⁻³ species. The new molecule was polymerized onto a glassy carbon electrode (GCE) to form thin films of different thickness, giving poly-10-AcMnODEAETPc-GCE, poly-20-AcMnODEAETPc-GCE and poly-30-AcMnODEAETPc-GCE, where 10, 20 and 30 represent the number of voltammetry scans during polymerization. Three distinct redox processes were observed on the modified electrode in 0.1 M phosphate buffer solution, pH 5, which confirmed the formation of the polymer. The current signal due to the herbicide, bentazon, was dependent on film thickness; the best signal was obtained on poly-20-AcMnODEAETPc-GCE while poly-10-AcMnODEAETPc-GCE gave the least signal. However, the signals due to the herbicide were better on the different films compared to the bare electrode. Electrochemical impedance spectroscopy (EIS) technique revealed that differences in film thickness offered different charge transfer resistances, R_ct, hence difference in current signals for bentazon oxidation were observed on these films. A Tafel slope of 77 mV/decade, obtained for the herbicide on poly-20-AcMnODEAETPc-GCE, denotes a fast one electron transfer followed by a slow chemical step in the electro-oxidation of bentazon. The voltammetry signals of the herbicide on the films indicated the likely involvement of ring-based redox processes in the detection of the herbicide. A plot of background corrected current response, on this film, versus the concentration of bentazon was linear within the range 50–750 μM with a detection limit of 2.48 × 10⁻⁷ M.     

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.     

Electrochemical study of chitosan films deposited from solution at reducing potentials

We report the electrochemical characterization of chitosan films deposited at gold electrodes from an acidic solution at reducing potentials. Cyclic voltammetry was used to characterize the deposition and electroactivity of chitosan coated gold electrodes. Chitosan films were found to deposit at gold electrodes at potentials more negative than −1.0 V versus Ag/AgCl, a potential associated with the onset of water reduction and increase in pH near the electrode. The chitosan films are electrochemically inactive; similar background charging currents are observed at bare gold and chitosan coated electrodes. The chitosan films are permeable to both cationic [Ru(NH₃)₆^3+/2+] and anionic [Fe(CN)₆^3−/4−] redox couples, but anionic complexes are retained in the chitosan film. Semiintegral analysis was used to examine adsorbed redox species at the chitosan coated electrode surface. Electrochemical parameters, including apparent diffusion coefficients for the redox probes at the electrodeposited chitosan modified electrodes are presented and are comparable to values reported for cast chitosan films.     

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.     

Surface properties of self-assembled monolayer films of tetra-substituted cobalt, iron and manganese alkylthio phthalocyanine complexes

Self-assembled monolayer (SAM) films of iron (SAM-1), cobalt (SAM-2) and manganese (SAM-3) phthalocyanine complexes, tetra-substituted with diethylaminoethanethio at the non-peripheral positions, were formed on gold electrode in dimethylformamide (DMF). Electrochemical, impedimentary and surface properties of the SAM films were investigated. Cyclic voltammetry was used to investigate the electrochemical properties of the films. Ability of the films to inhibit common faradaic processes on bare gold surface (gold oxidation, solution redox chemistry of [Fe(H₂O)₆]³⁺/[Fe(H₂O)₆]²⁺ and underpotential deposition (UDP) of copper) was investigated. Electrochemical impedance spectroscopy (EIS), using [Fe(CN)₆]^3−/4− redox process as a probe, offered insights into the electrical properties of the films/electrode interfaces. Surface properties of the films were probed using atomic force microscopy (AFM) and scanning electron microscopy (SEM). The films were employed for the electrocatalytic oxidation of the pesticide, carbofuran. Electrocatalysis was evidenced from enhanced current signal and less positive oxidation potential of the pesticide on each film, relative to that observed on the bare gold electrode. Mechanism of electrocatalytic oxidation of the pesticide was studied using rotating disc electrode voltammetry.     

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.     

Preparation,electrochemical, and spectroelectrochemical characterization of a new water-soluble copper phthalocyanine

A new water-soluble copper phthalocyanine, 2,9,16,23-tetrakis(4-(1-naphthoxy-4-sulfonic acid sodium salt)) phthalocyaninato copper NhtCuPc, where Nht indicates naphthoxy-4-sulfonic acid sodium salt, was synthesized and its electrochemical and spectroelectrochemical behavior were investigated in DMSO solution. The in situ spectroelectrochemical studies showed that the neutral complex exhibited the characteristic spectral changes corresponding to mono-anionic [NhtCuPc(3-)]⁻ and di-anionic [NhtCuPc(4-)]²⁻ species having long-term stability during reduction processes.     

Iodide/triiodide electrochemistry in ionic liquids: Effect of viscosity on mass transport, voltammetry and scanning electrochemical microscopy

The electrochemistry of I⁻/I₃⁻ was studied in ionic liquids using a combination of cyclic voltammetry, chronoamperometry and scanning electrochemical microscopy (SECM). The electrolytes were 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide [C_nC₁Im][Tf₂N], ionic liquids (where n = 2, 4 and 8) and I⁻ was typically added at a concentration of approximately 11 mM. During cyclic voltammetry, two sets of peaks were observed in each ionic liquid due to oxidation and reduction of the I⁻/I₃⁻ redox couple and oxidation/reduction of the I₃⁻/I₂ redox couple. The diffusion coefficients of I⁻ and I₃⁻, as determined using chronoamperometry, increased with increasing temperature and decreased with increasing ionic liquid viscosity. The effect of ionic liquid viscosity on ultramicroelectrode (UME) voltammetry was also determined using the I⁻/I₃⁻ redox couple. Steady-state behaviour was observed at 1.3 μm UMEs at slow voltammetric scan rates and steady-state SECM feedback approach curves were also obtained at a 1.3 μm Pt SECM tips, provided that the tip approach speed was sufficiently low.     

Solution and solid phase electrochemical behaviour of [Os(bpy)3]3[P2W18O62]

[Os(bpy)₃]₃[P₂W₁₈O₆₂] has been synthesised and characterised by elemental analysis, spectroscopic (UV-vis, IR spectroscopy) and electrochemical techniques. In 0.1 M Bu₄NPF₆ DMSO the complex shows a series of redox couples associated with the Os^3+/2+ and bipyridine ligands of the cationic [Os(bpy)₃]²⁺ moiety and the tungsten-oxo framework of the associated Dawson parent heteropolyanion, [P₂W₁₈O₆₂]⁶⁻. At this electrolyte concentration, the Os³⁺ redox form of the complex was seen to adsorb onto the electrode surface. When the electrolyte concentration is lowered to 0.01 M Bu₄NPF₆ in addition to the Os^3+/2+ redox couple, the redox process associated with the [P₂W₁₈O₆₂]^8−/7− couple also exhibited properties indicating surface based processes were present. Electroactive films of the complex were formed on carbon macroelectrodes by the redox switching of the transition metal within the complex. Voltammetric investigations into the film's behaviour in a range of buffer solutions (pH 2.0, 4.5 and 7.0) were performed. The films were found to possess better stability in acidic pH and the same pH dependence for the tungsten-oxo framework of the heteropolyanions as in solution. Solid state electrochemical measurements on mechanically attached microparticles of the complex were performed, with the effect of both the nature and concentration of the aqueous electrolyte on this behaviour being investigated. Upon redox switching between the Os^2+/3+ redox states, there is an associated insertion/expulsion of anions from/to the solution phase. Scanning electron micrographs of these solid state films were attained before and after redox cycling.