Cationic Species Research Articles

Synergistic effect of amine and borane in immobilized metallocene catalysts on ethylene polymerization

The effect of incorporating amines and borane into the supported metallocene catalyst systems was investigated for the polymerization of ethylene and copolymerization of ethylene-1-hexene. Two methods, the conventional method and the one-pot method, were employed to prepare immobilized metallocene catalysts. The synthesized catalysts underwent characterization using scanning electron microscopy (SEM), elemental analysis (EA), inductively coupled plasma (ICP) analysis, and X-ray photoelectron spectroscopy (XPS). The results revealed that the inclusion of polyethyleneimine (PEI) increased the Zr content in the catalyst and yielded polyethylene with higher molecular weight. PEI also exhibited the ability to enhance the comonomer response of supported metallocene catalysts. Additionally, the immobilization of both PEI and borane demonstrated a significant improvement in polymerization activity. XPS analysis demonstrated the electronic effects of amines and borane on the catalyst, indicating enhanced anionic properties of methylaluminoxane and the formation of cationic zirconocenium species. These findings suggest that the presence of PEI and borane promotes the formation of more active metallocene sites for ethylene polymerization.

Photoactivable alizarin and eugenol-based materials for antibacterial applications

We report herein the design of a new visible-light epoxy-based alizarin photosensitizer (AE) of iodonium salt (Iod) for the cationic polymerization (CP) of epoxidized eugenol monomers under visible-light irradiation. The combination of AE and Iod demonstrates highly efficient photoinitiating properties under air. As highlighted by fluorescence, laser flash photolysis (LFP) and electron paramagnetic resonance spin-trapping (ESR ST) experiments, AE acts as an electron donating molecule, and reacts with Iod under light exposure through its excited singlet and triplet states via a photoinduced electron transfer reaction, producing thus protonic acids, H+, able to initiate CP. Also, we demonstrate by EPR ST that the addition of diepoxy eugenol monomer may lead to the formation of reactive radical species which may be oxidized by Iod to form cationic species. Thus, new bio-based and photoactivable materials were designed by cationic photopolymerization with the use of alizarin-based photosensitizer and eugenol derived monomers. By tuning the weight proportion of eugenol derived epoxy monomers (mono- (EE) and di-epoxidized (EdE) eugenol), we can modulate the thermal and mechanical properties of the resulting materials. The new AE-based materials have demonstrated two interesting properties: first, the presence of EE in the polymer network has considerably decreased the number of colony forming units (CFUs) at the surface of materials whatever the bacterial strains used, and these samples demonstrate photoactivable properties as they produce, under visible-light irradiation, singlet oxygen, a biocide agent against bacteria. Interestingly, the irradiation of the AE/Iod/EE(50)/EdE(50) materials lead to a tremendous decrease of the number of E. coli and S. aureus CFUs at their surface. A reduction by 100% of the bacterial adhesion is observed upon visible-light exposure.

Proximity-Enabled Photochemical C-H Functionalization using a Covalent Organic Framework-Confined Fe2IV-μ-oxo Species in Water.

Water has been recognized as an excellent solvent for maneuvering both the catalytic activity and selectivity, especially in the case of heterogeneous catalysis. However, maintaining the active catalytic species in their higher oxidation states (IV/V) while retaining the catalytic activity and recyclability in water is an enormous challenge. Herein, we have developed a solution to this problem using covalent organic frameworks (COFs) to immobilize the (Et4N)2[FeIII(Cl)bTAML] molecules, taking advantage of the COF's morphology and surface charge. By using the visible light and [CoIII(NH3)5Cl]Cl2 as a sacrificial electron acceptor within the COF, we have successfully generated and stabilized the [(bTAML)FeIV-O-FeIV(bTAML)]- species in water. The COF backbone simultaneously acts as a porous host and a photosensitizer. This is the first time that the photochemically generated Fe2IV-μ-oxo radical cation species has demonstrated high catalytic activity with moderate to high yield for the selective oxidation of the unactivated C-H bonds, even in water. To enhance the catalytic activity and achieve good recyclability, we have developed a TpDPP COF film by transforming the TpDPP COF nanospheres. We have achieved the regio- and stereoselective functionalization of unactivated C-H bonds of alkanes and alkenes (3°:2° = 102:1 for adamantane with the COF film), which is improbable in homogeneous conditions. The film exhibits C-H bond oxidation with higher catalytic yield (32-98%) and a higher degree of selectivity (cis/trans = 74:1; 3°:2° = 100:1 for cis-decalin).

Sulfide-occluded zeolites: Cooperative adsorption-precipitation system for near perfect decontamination of aqueous Hg species

Sulfide-occluded zeolites could allow both adsorption reaction of zeolites and precipitation reaction of sulfides to operate within one system, which leads to synergic effects on removal of toxic cationic heavy metals from aqueous systems. Here we proved that near complete decontamination of aqueous Hg cations bellow WHO guideline level of 1 ppb could be accomplished with sulfide-occluded zeolites. Interestingly, adsorption of cationic Hg species resulted in the formation of discrete HgS crusts on the surfaces of the zeolite crystals. TEM and Hg removal isotherms strongly indicated that the HgS crust played a crucial role not only in preventing the back-release of adsorbed Hg species but also in scavenging residual aqueous Hg species. Therefore, in-situ cooperation of adsorption and precipitation reactions performed by sulfide-occluded zeolites could be applied to reliable and safe Hg decontamination of aqueous systems.

Structural and computational studies on a quenchable high-temperature polymorph of magnesium tungstate (MgWO4-II)

Single-crystals of a quenchable high-temperature polymorph of magnesium tungstate (MgWO4-II) have been grown using the flux method. Polycrystalline material of the same compound could be obtained from solid-state reactions performed at 1200 °C. Basic crystallographic data of the previously unknown modification are as follows: space group P1‾, a = 6.5525(6) Å, b = 7.5883(7) Å, c = 7.6976(6) Å, α = 119.064(9)°, β = 95.545(7)°, γ = 107.645(8)°, V = 304.84(5)3 Å and Z = 4. The crystal structure was solved from single-crystal diffraction using direct methods and refined to a residual value of R1 = 2.16%. Both cation species exhibit an octahedral oxygen coordination environment. By sharing common edges and corners, the octahedra form a three-dimensional network, which can be built from infinite rod-like elements running along [010] having a 2 × 2 octahedra wide cross section. MgWO4-II is topologically equivalent to the VO2(HT) structure-type. A detailed analysis of the relationships with other ABO4-compounds is presented. Solid-state characterization has been supplemented by micro-Raman spectroscopy. Interpretation of the spectroscopic data, including the allocation of the bands to certain vibrational species, has been aided by DFT-calculations. The thermal expansion tensor between ambient temperature and about 700 °C has been determined. The calculations indicate quasi-two-dimensional expansion behavior.

Synergistic Ion-Anchoring Passivation for Perovskite Solar Cells with Efficiency Exceeding 24% and Ultra-Ambient Stability.

The high-density defect states existing at the grain boundaries and heterojunction interfaces induce nonradiative charge recombination and ion migration processes within perovskite film, which seriously impair the device efficiency and stability. Here, we propose a novel synergistic ion-anchoring passivation (SIP) strategy for high-performance perovskite solar cells, by designing a multifunctional molecule to heal the charged defects via electrostatic interactions. The anion and cation species of the multifunctional molecule are rationally screened via high-throughput DFT simulation and experimental verification, which act as efficient surface passivation agents to heal the lead- and iodine-related defects. As a result, the defect-less perovskite films deliver encouraging device power conversion efficiency >24% with negligible hysteresis. A remarkable open-circuit voltage (Voc) of 1.17 V was obtained with a Voc deficit of 370 mV, featuring the outstanding defect-passivation capability of the SIP strategy. Moreover, the SIP-treated devices show exceptional ambient stability and maintain 70% of the initial efficiency after 150 h of high humidity exposure (relative humidity 70%-80%). Our results highlight the importance of the rational design of passivation agents to realize high-performance perovskite electronics.

Bifunctionality of Re Supported on TiO2 in Driving Methanol Formation in Low-Temperature CO2 Hydrogenation.

Low temperature and high pressure are thermodynamically more favorable conditions to achieve high conversion and high methanol selectivity in CO2 hydrogenation. However, low-temperature activity is generally very poor due to the sluggish kinetics, and thus, designing highly selective catalysts active below 200 °C is a great challenge in CO2-to-methanol conversion. Recently, Re/TiO2 has been reported as a promising catalyst. We show that Re/TiO2 is indeed more active in continuous and high-pressure (56 and 331 bar) operations at 125-200 °C compared to an industrial Cu/ZnO/Al2O3 catalyst, which suffers from the formation of methyl formate and its decomposition to carbon monoxide. At lower temperatures, precise understanding and control over the active surface intermediates are crucial to boosting conversion kinetics. This work aims at elucidating the nature of active sites and active species by means of in situ/operando X-ray absorption spectroscopy, Raman spectroscopy, ambient-pressure X-ray photoelectron spectroscopy (AP-XPS), and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Transient operando DRIFTS studies uncover the activation of CO2 to form active formate intermediates leading to methanol formation and also active rhenium carbonyl intermediates leading to methane over cationic Re single atoms characterized by rhenium tricarbonyl complexes. The transient techniques enable us to differentiate the active species from the spectator one on TiO2 support, such as less reactive formate originating from spillover and methoxy from methanol adsorption. The AP-XPS supports the fact that metallic Re species act as H2 activators, leading to H-spillover and importantly to hydrogenation of the active formate intermediate present over cationic Re species. The origin of the unique reactivity of Re/TiO2 was suggested as the coexistence of cationic highly dispersed Re including single atoms, driving the formation of monodentate formate, and metallic Re clusters in the vicinity, activating the hydrogenation of the formate to methanol.

Alkali metal cations modulate the geometry of different binding sites in HCN4 selectivity filter for permeation or block.

Hyperpolarization-activated cyclic-nucleotide gated (HCN) channels are important for timing biological processes like heartbeat and neuronal firing. Their weak cation selectivity is determined by a filter domain with only two binding sites for K+ and one for Na+. The latter acts as a weak blocker, which is released in combination with a dynamic widening of the filter by K+ ions, giving rise to a mixed K+/Na+ current. Here, we apply molecular dynamics simulations to systematically investigate the interactions of five alkali metal cations with the filter of the open HCN4 pore. Simulations recapitulate experimental data like a low Li+ permeability, considerable Rb+ conductance, a block by Cs+ as well as a punch through of Cs+ ions at high negative voltages. Differential binding of the cation species in specific filter sites is associated with structural adaptations of filter residues. This gives rise to ion coordination by a cation-characteristic number of oxygen atoms from the filter backbone and solvent. This ion/protein interplay prevents Li+, but not Na+, from entry into and further passage through the filter. The site equivalent to S3 in K+ channels emerges as a preferential binding and presumably blocking site for Cs+. Collectively, the data suggest that the weak cation selectivity of HCN channels and their block by Cs+ are determined by restrained cation-generated rearrangements of flexible filter residues.

Biosorption of Fe (II) and Pb (II) on unmodified Senna tora: Isotherm and kinetic modeling

Contamination of environment by heavy metals has become a major concern worldwide. The role of conventional methods in remediating heavy metals has become ineffective and costly. Therefore, it becomes imperative to explore bioremediation using a cost effective, efficient and environmentally friendly alternative method of removing heavy metals. In this study, the adsorption behaviour of Senna tora, a low-cost adsorbents, with respect to Fe(II) and Pb(II) ions, has been studied in order to consider its application to the treatment of wastewater. The physicochemical properties of the unmodified Senna tora were predetermined. The batch experimental method was employed: parameters such as pH, contact time, dosage and initial metal concentration were studied. The influence of the pH of the metal ion solutions on the uptake levels of the metal ions by the adsorbent used was carried out between pH 4 and 10. The optimum pH for both Fe (II) and Pb(II) removals by Senna tora was 7. An equilibrium contact time of 60 min was required for the adsorption of Pb(II) ions onto Senna tora. Percentage sorption of Fe(II) increased from 94 to 99% and that of Pb (II) from 94.4 to 96% as adsorbent dose was increased from 2 to 10 g. The isotherms data provide information on the capacity of the adsorbent or the amount required to remove a unit mass of pollutant under the operating conditions. The equilibrium data of Fe(II) and Pb(II) adsorbed onto Senna tora pods were fitted by the Langmuir, Freundlich, and Temkin isotherms. On the basis of correlation coefficients R2, it is concluded that the Fe(II) and Pb(II) biosorption is better fitted to the Freundlich model. This suggests that the biosorption of Fe(II) and Pb(II) on the surface of Senna tora pods occurs on heterogeneous binding sites with equivalent adsorption energies and multilayer coverage. The results demonstrated that Senna tora pod holds potential to remove cationic heavy metal species from industrial wastewater.

Facile Metal Release from Pore-Lining Phases Enables Unique Carbonate Zonation in a Basalt Carbon Mineralization Demonstration.

Carbon-negative strategies such as geologic carbon sequestration in continental flood basalts offers a promising route to the removal of greenhouse gases, such as CO2, via safe and permanent storage as stable carbonates. This potential has been successfully demonstrated at a field scale at the Wallula Basalt Carbon Storage Pilot Project where supercritical CO2 was injected into the Columbia River Basalt Group (CRBG). Here, we analyze recovered post-injection sidewall core cross-sections containing carbonate nodules using μ-XRF chemical mapping techniques that revealed compositional zonation within the nodules. The unique nature of the subsurface anthropogenic carbonates is highlighted by the near absence of Mg in an ankerite-like composition. Furthermore, a comparison between pre- and post-injection sidewall cores along with an in-depth chemical mapping of basalt pore lining cements provides a better understanding into the source and fate of critical cationic species involved in the precipitation of carbon mineralization products. Collectively, these results provide crucial insights into carbonate growth mechanisms under a time-dependent pore fluid composition. As such, these findings will enable parameterization of predictive models for future CO2 sequestration efforts in reactive reservoirs around the world.

A molecular dynamics study on ionic current rectification of ultra-narrow conical nanopore

Understanding the ionic current rectification (ICR) is crucial for elucidating the physical mechanisms of ions transport in various processes and for advancing the development of nanodevices. Using molecular dynamics simulations, we explore the properties of ionic motion in negatively charged conical nanopores with a tip radius fixed at 1.51 nm. The effects of ion transport behavior on ICR under different electric fields, angles, and cation species were studied. The rectification ratio increases linearly with an increase in angle (0–15°), slows down and then eventually stabilizes with an increase in electric fields, and depends on the cation species being used. Our results indicate that the ion current is mainly contributed by the flow of cations in ultra-narrow nanopores. Further analysis of the ion concentration distribution reveals that the inverse ICR phenomenon is mainly caused by the cation concentration polarization at the tip under negative electric field, making cations are difficult to enter the nanopore from the tip, resulting in a decrease in ionic current. Additionally, cations entering the nanopore from the tip become trapped in the potential well of the tip at a negative electric field, leading to lower ion mobility and ionic current. Finally, it is found the difference in ICR ratio mainly results from the migration rate of cations with different nanopore angles and different ionic types. Our study provides valuable insights into the behavior of ions in ultra-narrow conical nanopores and the mechanisms behind ICR, which could guide the design and development of nanodevices that rely on ionic transport, such as biosensors and energy storage systems.

Highly Electrophilic Mononuclear Cationic Aluminum Alkoxide Complexes: Syntheses, Reactivity and Catalytic Applications.

Herein, we report on the synthesis of β-diketiminate supported aluminum complexes bearing terminal alkoxide and mono-thiol functional groups: LAlOMe(Et) (2), LAlOtBu(Et) (3), and LAlSH(Et) (4), (L= [HC{C(Me)N-(2,6-iPr2C6H3)}2]). Complexes 2 and 3 are further utilized as synthons to generate some fascinating cationic aluminum alkoxide complexes, [LAlOMe(µ-OMe)-Al(Et)L][EtB(C6F5)3] (5), [LAlOMe(OEt2)][EtB(C6F5)3] (6), and [LAlOtBu(OEt2)][EtB(C6F5)3] (8). These electrophilic cationic species are well characterized by spectroscopic and crystallographic techniques. The assessment of Lewis acidity by the Gutmann-Beckett method revealed superior Lewis acidity of the cations substituted with electron demanding alkoxy groups in comparison to the known methyl analogue [LAlMe][B(C6F5)4]. This has been further endorsed by computational calculations to determine the NBO charges and hydride ion affinity for complexes 6 and 8. These complexes are also capable of activating triethylsilane in stoichiometric reactions. The applicability of these complexes has been realized in the hydrosilylation of ethers, carbonyls, and olefines. Additionally, the solid state structure of a new THF stabilized aluminum halide cation [LAlCl(THF)][B(C6F5)4] (11) has also been reported.

Synthesis of cationic N-methylated chlorophyll derivatives and C3-substitution effect on their optical properties

Methyl N22-methyl-pyropheophorbides possessing various substituents at the C3-position were prepared by modifying natural chlorophyll-a. Their syntheses were based on the regioselective N22-methylation of a chlorin π-system and/or the functionalization of the C3-substituents in the resulting N22-methyl-chlorins. The synthetic N22-methyl-chlorins were obtained as cationic species due to their high basicity. The N22-methylation largely affected the ultraviolet–visible absorption and fluorescence emission spectra and especially moved the Qy absorption and intense emission maxima to shorter wavelengths and the Qx and intense Soret maxima to longer wavelengths. The C3-substitution effect on the redmost absorption and bluemost emission maxima in the N22-methyl-chlorins was smaller than that in the N22-unsubstitutes. In most cases, the N22-methylation increased the Stokes shifts and decreased the fluorescence emission quantum yields and lifetimes, which were ascribable to the flexibility of the distorted N22-methyl-chlorin π-planes.

One-pot Synthesis of Helical Azaheptalene and Chiroptical Switching of an Isolable Radical Cation.

A nitrogen-centered heptalene, azaheptalene, was designed as a representative of a new class of redox-responsive molecules with a large steric strain that originates from the adjacent seven-membered rings. The pentabenzo derivative of azaheptalene was efficiently synthesized by a palladium-catalyzed one-pot reaction of commercially available reagents. Bromination led to mono- and dibrominated derivatives, the latter of which is interconvertible with isolable radical cation species exhibiting near-infrared absorption. Since the azaheptalene skeleton shows configurationally stable helicity with a large torsion angle, enantiomers could be successfully separated. Thus, optically pure azaheptalenes with P- or M-helicity showed strong chiroptical properties (|gabs| ≥ 0.01), which could be changed by an electric potential.

Pd/C-Based Sensor for Gas Sensing in Transformer Oil

The detection of dissolved gas in transformer oil is of vital importance to diagnose the early fault and monitor the security and stability of power systems. In this work, distinct Pd/C, Pd/C-R and Pd/NC were synthesized and evaluated. XRD and XPS characterizations show that both Pd0 and PdII are presented over the surface of carbon host for Pd/C, while poor gas-sensitive properties were presented for Pd0 in H2-reduced Pd/C-R sample. High content of cationic PdII species are synthesized by nitrogen doping of the carbon surface for Pd/NC. The experimental results showed that the gas-sensitive performances of H2/CO/C2H2 gases is facilitated over the developed Pd/NC material. This study can provide reference for the rapid detection and fault diagnosis of faulty gases in transformers.

Oxidation of 5,15-Dioxaporphyrin: Its Generality and Novelty as an Oxaporphyrin Analogue.

5,15-Dioxaporphyrin (DOP) is a novel meso-oxaporphyrin analogue and exhibits unique 20π-antiaromaticity, unlike its mother congener of 18π-aromatic 5-oxaporphyrin, commonly known as its cationic iron complex called verdohem, which is a key intermediate of heme catabolism. To reveal its reactivities and properties as an oxaporphyrin analogue, the oxidation of tetra-β-arylated DOP (DOP-Ar4 ) was explored in this study. Stepwise oxidation from the 20π-electron neutral state was achieved, and the corresponding 19π-electron radical cation and 18π-electron dication were characterized. Further oxidation of the 18π-aromatic dication resulted in the formation of a ring-opened dipyrrindione product by hydrolysis. Considering a similar reaction of verdoheme to ring-opened biliverdin in the heme degradation in nature, the current result consolidates the ring-opening reactivity of oxaporphyrinium cation species.

Oxidation of 5,15‐Dioxaporphyrin: Its Generality and Novelty as an Oxaporphyrin Analogue

Abstract5,15‐Dioxaporphyrin (DOP) is a novel meso‐oxaporphyrin analogue and exhibits unique 20π‐antiaromaticity, unlike its mother congener of 18π‐aromatic 5‐oxaporphyrin, commonly known as its cationic iron complex called verdohem, which is a key intermediate of heme catabolism. To reveal its reactivities and properties as an oxaporphyrin analogue, the oxidation of tetra‐β‐arylated DOP (DOP‐Ar4) was explored in this study. Stepwise oxidation from the 20π‐electron neutral state was achieved, and the corresponding 19π‐electron radical cation and 18π‐electron dication were characterized. Further oxidation of the 18π‐aromatic dication resulted in the formation of a ring‐opened dipyrrindione product by hydrolysis. Considering a similar reaction of verdoheme to ring‐opened biliverdin in the heme degradation in nature, the current result consolidates the ring‐opening reactivity of oxaporphyrinium cation species.

Unveiling the Influence of Hydrated Deep Eutectic Solvents on the Dynamics of Water-Soluble Proteins.

Deep eutectic solvents (DESs) are mixtures of two or more pure compounds (e.g., Lewis or Brønsted acids and bases, anionic and/or cationic species) in a well-defined stoichiometric proportion, with a melting point lower to that of an ideal liquid mixture. These neoteric solvents are highly tunable through varying the structure or relative ratio of parent components and have been evaluated as solvents able to improve biomolecules' performance, specifically their stability and biocatalytic properties. Inspired by a recent crystallographic study, we have explored through molecular dynamics (MD) simulations the dynamic properties of two different proteins (hen egg-white lysozyme and the human VH antibody fragment HEL4) in a (20% w/w) hydrated solution of choline chloride-glycerol (1:2). We have developed proper force fields to account for DES, protein, and DES-protein interactions, which have been calibrated using pair distribution function measurements of pure DES solutions. MD results show that the presence of DES quenches the protein motion, increasing the rigidity of the overall protein structure. Specific interactions among DES components and protein residues, such as those between choline ions and two Tryptophan residues of lysozyme, may amplify the protein-DES interactions and lead to protein crystallization in the presence of hydrated DES. These findings open new horizons to improve or achieve control on protein properties by a proper choice of hydrated DESs used as solvents.

Synthesis and crystal structure of a bench-stable pyridinium ketene hemiaminal: 1-(1-eth-oxy-ethen-yl)-2-[meth-yl(phen-yl)amino]-pyridin-1-ium tri-fluoro-methane-sulfonate.

The novel bench-stable N-quaternized ketene N,O-acetal, C16H19N2O+·CF3O3S-, was synthesized and its structure determined. The title compound is a rare example of a pyridinium ketene hemiaminal for which a crystal structure has been determined, joining the 2-chloro-1-(1-ethyoxyethen-yl)pyridin-1-ium tri-fluoro-methane-sulfonate salt from which it was synthesized. The cationic species of the title compound can be defined by three individually planar fragments assembling into a non-coplanar cation. The phenyl substituent extending from the amino nitro-gen atom and the ethyoxyvinyl substituent extending from the pyridine N atom are oriented on the same side of the mol-ecule and maintain the closest coplanar relationship of the three fragments. Supra-molecular inter-actions are dominated by C-H⋯O inter-actions from the cation to the SO3 side of the tri-fluoro-methane-sulfonate anion, forming a two-dimensional substructure.

Electrochemical and In-situ spectroelectrochemical properties of novel mononuclear 2,4-di-tert-butyl-6-(3,4-dicyanophenoxy)phenolate substituted metallophthalocyanine compounds

In this study, the synthesis and characterization of a series of novel tetra substituted highly soluble metallophthalocyanines [M = CoII, FeIII, MnIII, NiII and ZnII] derivatives bearing 2,4-di-tert-butyl-6-(3,4-dicyanophenoxy)phenolate groups on the peripheral positions are reported. These phthalocyanine (Pc) compounds can be used as new starting materials for the synthesis of dinuclear ball-type Pcs due to the involvement of four phthalonitrile rings as closable end groups in their molecules. The assignment of the redox processes of these compounds indicated that CoII, FeIII, and MnIII centers into the Pc core increased the redox richness of the complexes, with the addition of metal-based electron transfer processes to the ring-based ones while NiPc and ZnPc show only ring-based electron transfer processes. These ball-type Pc precursor compounds exhibited a unique character also as a result of eight redox-active nitrile end groups on the peripheral tails of the Pc core. Thus, electrochemical and spectroelectrochemical properties of metallophthalocyanine complexes were analysed, also in comparison to their previously reported (5-(tert-butyl)-2-((3,4-dicyanophenoxy)methyl)phenyl)methanolate substituted analogues to determine the influence of metal centers and substituents in the periphery. Altering the metal center of the Pc ring as incorporation of a redox active metal center and changing the positions of the substituents slightly affected the potentials for nitrile and Pc ring redox processes. However, the spectral and color responses of the complexes were significantly influenced by the nature of central metal and peripheral substituents. As an important reflection, the electron transfer processes of the complexes and the connection between the electrochemically generated anionic and cationic species originated distinct spectral and color changes, identified with in-situ spectroelectrochemical measurements in solution medium. These measurements pointed out their potential applicability in the fields of the opto electronic technologies.