Porphyrin Layers Research Articles

Porphyrin-Sensitizers and Anthracene-Annihilators Built in Isostructural Frameworks for Investigating Triplet-Triplet Annihilation Upconversion.

In this study, four isostructural pillar-layered frameworks were constructed using a porphyrin layer and an anthracene pillar, which served as the sensitizer and annihilator, respectively, in the triplet-triplet annihilation upconversion (TTA-UC) system. Framework 1 demonstrated the highest upconversion quantum yield of 1.01%. Additionally, 1 and 2 also exhibited down-conversion fluorescence resulting from the porphyrin component. A twist intramolecular charge transfer (TICT) state was observed in the bianthracene chromophore of 2, resulting in transient rotation of two anthracene rings and red-shifted emission. Both computational studies and experiments confirmed the transition from a locally excited state to a TICT state upon the inclusion of polar guest molecules into the framework.

Porphene and porphite as porphyrin analogs of graphene and graphite

Two-dimensional materials have unusual properties and promise applications in nanoelectronics, spintronics, photonics, (electro)catalysis, separations, and elsewhere. Most are inorganic and their properties are difficult to tune. Here we report the preparation of Zn porphene, a member of the previously only hypothetical organic metalloporphene family. Similar to graphene, these also are fully conjugated two-dimensional polymers, but are composed of fused metalloporphyrin rings. Zn porphene is synthesized on water surface by two-dimensional oxidative polymerization of a Langmuir layer of Zn porphyrin with K2IrCl6, reminiscent of known one-dimensional polymerization of pyrroles. It is transferable to other substrates and bridges μm-sized pits. Contrary to previous theoretical predictions of metallic conductivity, it is a p-type semiconductor due to a predicted Peierls distortion of its unit cell from square to rectangular, analogous to the appearance of bond-length alternation in antiaromatic molecules. The observed reversible insertion of various metal ions, possibly carrying a fifth or sixth ligand, promises tunability and even patterning of circuits on an atomic canvas without removing any π centers from conjugation.

Porphyrinoids-Junctions Based Chemical Sensors

The three main elements that form the porphyrinoids (aromatic ring, metal atom, and lateral compounds) provide the key to direct the chemical reactivity of the molecule towards desired classes of compounds. This property gives rise to a manifold of molecular architectures each with distinct features, that, in many cases, make them suitable for technological applications, among the others, chemical sensing.The gas sensing properties of porphyrinoids involves the interaction with airborne molecules [1,2]. These are driven by a multiplicity of mechanisms including hydrogen bond, Van der Waals forces, and coordination that are active at once. Coordinating molecules, such as amines, have a preferential absorption onto porphyrins solid state layers, however the response to other molecules is not negligible so, eventually porphyrin sensors are seldom selective. However, the pattern of sensitivity strongly depends on slight changes in the molecular structure. This facilitate the development of sensor arrays that can easily implement the combinatorial selectivity principle of olfaction [3]. This property has been exploited to prepare electronic noses for various applications, not least medical diagnosis from the analysis of the volatile portion of the human metabolites [4–6].These results were obtained coating with porphyrin layers the surface of quartz microbalance sensors. These are mass sensitive piezoelectric devices where the crystal resonance frequency is matched with the electric resonance. Mass sensors are quite suitable to prepare sensors that preserve the global sensitivity pattern of porphyrinoids, thus enabling an efficient combinatorial selectivity suitable for those applications which are characterized by patterns of volatile compounds. In spite of these positive properties, quartz microbalances are bulky and costly devices not suitable for low-costs, miniaturized devices. Thus, the current challenge is the development of impedance-based sensors that can preserve the wide sensitivity pattern of porphyrinoids.To this regard, we have been interested to study the combination of porphyrnoids with conductive materials such as inorganic, and organic semiconductors.In this presentation some relevant results will be present in particular about porphyrinoids coated ZnO nanostructures [7], the functionalization of the internal surface of face-masks with blends of porphyrinoids and PEDOT [8]and the heterojunctions formed by corrole polymer and phthalocyanine [9]. The sensitivity patterns of these devices approaches the behavior of quartz microbalance sensors paving the way for an effective large-scale deployment of porphyrinoids based artificial olfaction systems.Reference[1] R. Paolesse, Porphyrinoids for Chemical Sensor Applications, Chem. Rev. 117 (2017) 2517–2583.[2] C. Di Natale, C.P. Gros, R. Paolesse, Corroles at work: a small macrocycle for great applications, Chem. Soc. Rev. 51 (2022) 1277–1335.[3] I. Manzini, D. Schild, Di Natale C., Principles of odor coding in vertebrates and artificial chemosensory systems, Physiol. Rev. 102 (2022) 61–154.[4] R. Gasparri, R. Capuano, A. Guaglio, V. Caminiti, F. Canini, A. Catini, G. Sedda, R. Paolesse, C. Di Natale, L. Spaggiari, Volatolomic urinary profile analysis for diagnosis of the early stage of lung cancer, J. Breath Res. 16 (2022).[5] Y.K. Mougang, L. Di Zazzo, M. Minieri, R. Capuano, A. Catini, J.M. Legramante, R. Paolesse, S. Bernardini, C. Di Natale, Sensor array and gas chromatographic detection of the blood serum volatolomic signature of COVID-19, IScience. 24 (2021) 102851.[6] M. Murdocca, F. Torino, S. Pucci, M. Costantini, R. Capuano, C. Greggi, C. Polidoro, G. Somma, V. Pasqualetti, Y. Ketchanji Mougang, A. Catini, G. Simone, R. Paolesse, A. Orlandi, A. Mauriello, M. Roselli, A. Magrini, G. Novelli, C. Di Natale, F.C. Sangiuolo, Urine LOX-1 and Volatilome as Promising Tools towards the Early Detection of Renal Cancer, Cancers (Basel). 13 (2021) 4213.[7] G. Magna, M. Muduganti, M. Stefanelli, Y. Sivalingam, F. Zurlo, E. Di Bartolomeo, A. Catini, E. Martinelli, R. Paolesse, C. Di Natale, Light-Activated Porphyrinoid-Capped Nanoparticles for Gas Sensing, ACS Appl. Nano Mater. 4 (2021) 414–424.[8] L. Di Zazzo, G. Magna, M. Lucentini, M. Stefanelli, R. Paolesse, C. Di Natale, Sensor-embedded face masks for detection of volatiles in breath: A proof of concept study, Chemosensors. 9 (2021).[9] L. Di Zazzo, A. Kumar, R. Meunier-Prest, C. Di Natale, R. Paolesse, M. Bouvet, Electrosynthesized copper polycorroles as versatile materials in double lateral heterojunctions (submitted) 2022.

Graphdiyne-porphyrin composite materials GDY/Por and Por@GDY for lithium ion battery anodes

Due to the structure containing sp-/sp2-hybridized carbon atoms and porous property, graphdiyne (GDY) is predicted and demonstrated as a novel anode material in lithium-ion batteries. In this paper, two different graphdiyne-porphyrin composite materials (GDY/Por and Por@GDY) were prepared by the reaction of the precursors hexaethynylbenzene and 5,10,15,20-tetrakis(4-tert-butylphenyl)porphyrin or 5,10,15,20-(tetra-4-ethynyphenyl)porphyrin, result in the out-of-plane GDY/Por material through π–π interaction or in-plane conjugated Por@GDY structure. When the as-prepared graphdiyne-porphyrin composite materials were used as anodes for lithium-ion batteries, GDY/Por exhibited more excellent electrochemical performance in capacity, rate performance, and cycling stability than that of Por@GDY. Combined with the theoretical calculations, the improvement can be ascribed to the larger specific surface area as well as the well-defined nitrogen active sites and the organic porphyrin layer intercalation in GDY/Por, which probably led to the interlayer expansion and the increase of the lithium storage ability.

Spectroscopic fingerprints of iron-coordinated cobalt and iron porphyrin layers on graphene

Spectroscopic fingerprints of iron-coordinated cobalt and iron porphyrin layers on graphene

Building large-scale unimolecular scaffolding for electronic devices

The fabrication of a future generation of (opto)electronic devices based on molecular components and materials will require careful chemical design, coupled with assembly methods that permit precise spatial orientation and arrangement of the functional molecules within device structures. Although unimolecular electronics are already a laboratory reality, the variation in the arrangement of the molecule within a molecular junction from measurement to measurement is considerable. Consequently, controlling the precise geometry at the molecule–metal contacts is a long-standing and largely unresolved challenge. Here, a strategy to fabricate uniform unimolecular junctions distributed in a regular pattern is reported. A monolayer of zinc metalloporphyrins, peripherally functionalised by bulky dendrons, is used to provide a well-defined array of molecular binding sites with precise spatial distribution. The dendrons are then photochemically cross-linked to form a robust base-layer. Parallel, uniformly-spaced unimolecular structures are subsequently assembled on these binding sites through a layer-by-layer (LbL) strategy. This LbL strategy proceeds through coordination of an α,ω-amino functionalised oligo(phenylene)ethynylene (OPE) molecule to the zinc ions of the metalloporphyrin template base-layer. The structure is then extended through alternating self-assembled layers of (cross-linked) zinc porphyrin and OPE. The coordination interaction between the zinc(II) sites and the bifunctional OPE wire ensures a high degree of registry between the layers and good electrical contact through the extended arrays and offer fine control over the chemical composition.

Efficient Decrease in Corrosion of Steel in 0.1 M HCl Medium Realized by a Coating with Thin Layers of MnTa2O6 and Porphyrins Using Suitable Laser-Type Approaches.

The purpose of this research is to meet current technical and ecological challenges by developing novel steel coating systems specifically designed for mechanical equipment used in aggressive acid conditions. Homogeneous sandwich-type layered films on the surface of steel electrodes were realized using a pseudo-binary oxide, MnTa2O6, and two different substituted porphyrin derivatives, namely: 5-(4-carboxy-phenyl)-10,15,20-tris (4-methyl-phenyl)-porphyrin and 5-(4-methyl-benzoate)-10,15,20-tris (4-methyl-phenyl)-porphyrin, which are novel investigated compound pairs. Two suitable laser strategies, pulsed laser deposition (PLD) and matrix-assisted pulsed laser evaporation (MAPLE), were applied in order to prevent porphyrin decomposition and to create smooth layers with low porosity that are extremely adherent to the surface of steel. The electrochemical measurements of corrosion-resistant coating performance revealed that in all cases in which the steel electrodes were protected, a significant value of corrosion inhibition efficiency was found, ranging from 65.6 to 83.7%, depending on the nature of the porphyrin and its position in the sandwich layer. The highest value (83.7%) was obtained for the MAPLE/PLD laser deposition of 5-(4-carboxy-phenyl)-10,15,20-tris (4-methyl-phenyl)-porphyrin/MnTa2O6(h), meaning that the inhibitors adsorbed and blocked the access of the acid to the active sites of the steel electrodes.

Systematic study of precursor effects on structure and oxygen reduction reaction activity of FeNC catalysts.

In this work, the effect of porphyrin loading and template size is varied systematically to study its impact on the oxygen reduction reaction (ORR) activity and selectivity as followed by rotating ring disc electrode experiments in both acidic and alkaline electrolytes. The structural composition and morphology are investigated by 57Fe Mössbauer spectroscopy, transmission electron microscopy, Raman spectroscopy and Brunauer-Emmett-Teller analysis. It is shown that with decreasing template size, specifically the ORR performance towards fuel cell application gets improved, while at constant area loading of the iron precursor (here expressed in number of porphyrin layers), the iron signature does not change much. Moreover, it is well illustrated that too large area loadings result in the formation of undesired side phases that also cause a decrease in the performance, specifically in acidic electrolyte. Thus, if the impact of morphology is the focus of research it is important to consider the area loading rather than its weight loading. At constant weight loading, beside morphology the structural composition can also change and impact the catalytic performance. This article is part of the theme issue 'Bio-derived and bioinspired sustainable advanced materials for emerging technologies (part 2)'.

Silver Nanoparticles Decorated with PEGylated Porphyrins as Potential Theranostic and Sensing Agents.

Silver nanoparticles (AgNPs) stand out over other metal nanoparticles thanks to their peculiar bactericidal and spectroscopic properties. Tunability of the AgNPs chemical–physical properties could be provided through their organic covalent coating. On the other hand, PEGylated porphyrin derivatives are versatile heteromacrocycles investigated for uses in the biomedical field as cytotoxic and tracking agents, but also as sensors. In this work, an easy multi-step approach was employed to produce coated silver nanoparticles. Specifically, the AgNPs were functionalized with 5,10,15-[p-(ω-methoxy-polyethyleneoxy)phenyl]-20-(p-hydroxyphenyl)-porphyrin (P(PEG350)3), using chloropropanethiol as a coupling agent. The P(PEG350)3 was structurally characterized through MALDI-TOF mass spectrometry, NMR spectroscopy and thermal analyses. The functionalization of AgNPs was monitored step-by-step employing UV-Vis spectroscopy, dynamic light scattering and thermogravimetric techniques. HRTEM and STEM measurements were used to investigate the morphology and the composition of the resulting nanostructured system (AgNP@P(PEG350)3), observing a long-range alignment of the outer porphyrin layer. The AgNP@P(PEG350)3 combines the features of the P(PEG350)3 with those of AgNPs, producing a potential multifunctional theranostic tool. The nanosystem revealed itself suitable as a removable pH sensor in aqueous solutions and potentially feasible for biological environment applications.

Wet-Chemically Prepared Porphyrin Layers on Rutile TiO2(110).

Porphyrins are large organic molecules that are interesting for different applications, such as photovoltaic cells, gas sensors, or in catalysis. For many of these applications, the interactions between adsorbed molecules and surfaces play a crucial role. Studies of porphyrins on surfaces typically fall into one of two groups: (1) evaporation onto well-defined single-crystal surfaces under well-controlled ultrahigh vacuum conditions or (2) more application-oriented wet chemical deposition onto less well-defined high surface area surfaces under ambient conditions. In this study, we will investigate the wet chemical deposition of 5-(monocarboxyphenyl)-10,15,20-triphenylporphyrin (MCTPP) on well-defined rutile TiO2(110) single crystals under ambient conditions. Prior to deposition, the TiO2(110) crystals were also cleaned wet-chemically under ambient conditions, meaning none of the preparation steps were done in ultrahigh vacuum. However, after each preparation step, the surfaces were characterized in ultrahigh vacuum with X-ray photoelectron spectroscopy (XPS) and the result was compared with porphyrin layers prepared in ultrahigh vacuum (UHV) by evaporation. The differences of both preparations when exposed to zinc ion solutions will also be discussed.

Non-Covalent Postfunctionalization of Dye Layers on TiO2 - A Tool for Enhancing Injection in Dye-Sensitized Solar Cells.

We report on newly tailored dye layers, which were employed, on one hand, for covalent deposition and, on the other hand, for non‐covalently post‐functionalizing TiO2 nanoparticle films. Our functionalization concept enabled intermixing a stable covalent attachment of a first layer with a highly versatile and reversible hydrogen bonding through the Hamilton receptor–cyanuric acid binding motif as a second layer. Following this concept, we integrated step‐by‐step a first porphyrin layer and a second porphyrin/BODIPY layer. The individual building blocks and their corresponding combinations were probed with regard to their photophysical properties, and the most promising combinations were implemented in dye‐sensitized solar cells (DSSCs). Relative to the first porphyrin layer adding the second porphyrin/BODIPY layers increased the overall DSSC efficiency by up to 43 %.

An In-Depth Assessment of the Electronic and Magnetic Properties of a Highly Ordered Hybrid Interface: The Case of Nickel Tetra-Phenyl-Porphyrins on Fe(001)-p(1 × 1)O.

In this paper we focus on the structural, electronic, and magnetic properties of Ni tetra-phenyl-porphyrins (NiTPP) grown on top of Fe(001)–p(1 × 1)O. Ordered thin films of metal TPP molecules are potentially interesting for organic electronic and spintronic applications, especially when they are coupled to a ferromagnetic substrate. Unfortunately, porphyrin layers deposited on top of ferromagnetic substrates do not generally show long-range order. In this work, we provide evidence of an ordered disposition of the organic film above the iron surface and we prove that the thin layer of iron oxide decouples the molecules from the substrate, thus preserving the molecular electronic features, especially the HOMO-LUMO gap, even when just a few organic layers are deposited. The effect of the exposure to molecular oxygen is also investigated and an increased robustness against oxidation with respect to the bare substrate is detected. Finally, we present our results for the magnetic analysis performed by spin resolved spectroscopy, finding a null magnetic coupling between the molecules and the substrate.

Simple lattice model of self-assembling metal-organic layers of pyridyl-substituted porphyrins and copper on Au(111) surface.

A simple lattice model of metal-organic adsorption layers self-assembling on a Au(111) surface and based on pyridyl-substituted porphyrins differing in the number of functional groups and their position has been proposed. The model has been parameterized using DFT methods. The ground state analysis of the considered model demonstrates the variety of surface-confined metal-organic networks (SMONs) containing square, linear, and discrete elements appearing in the adsorption layer depending on the partial pressure of the components. The SMONs comprising more symmetrical molecules with a greater number of pyridyl substituents in the porphyrin core exhibit more diverse phase behavior. Structures of the phase diagrams were verified at nonzero temperatures using Grand Canonical Monte Carlo simulations. It was found that the continuous SMONs have higher thermal stability at relatively low partial pressures of the organic component, while the linear and discrete SMONs are more thermally stable at high pressure. Depending on the partial pressure of the organic component, thermal destruction of continuous SMONs occur either through the formation of defects/islands having structures of the linear SMONs, or through the sublimation of individual structural elements. Melting of linear SMONs reveals the appearance of 2D pores or islands of a purely organic phase. The latter fact is confirmed by the experimentally observed coexistence of these phases.

Close-Packed Arrangements of Flat-On Free-Base Porphyrins Driven by van der Waals Epitaxy

The functionality of low dimensional phases of porphyrins in optical, chemical, electrical, and multimodal combinational devices is strictly related to the control of molecular orientation within the produced solid layers. A promising strategy to drive the growth of adlayers with predictable structural properties relies on the template effect exerted by the substrate. Tetraphenyl porphyrins, being disc-shaped objects, can be adsorbed on a crystal surface by taking on different geometries. An edge-on configuration is adopted when the interactions among molecules overtake those between molecules and substrate, whereas a flat-on configuration is adopted when molecule-substrate interaction is dominant, with the weaker intermolecular interaction driving a close-packed geometry in the adlayer. For this latter reason, square and/or hexagonal lattice symmetries of physisorbed porphyrin layers are disclosed on highly interacting metal substrates such as Au(111). Unfortunately, metal substrates modify the intrinsic properties of porphyrins by suppressing many of their functionalities. To overcome this drawback, here we report the selective growth of porphyrins in a flat-on arrangement on the chiral (110) cleavage surface of the mixed molecular organic crystal formed by 2,5-diketopiperazine and fumaric acid in a 1:1 mole ratio. The energetic advantage ensured by the interaction with the insulating substrate drives the prevalent formation of domains with a square symmetry, which is retained from monolayer to multilayers. However, rare domains with a hexagonal symmetry are revealed and analyzed by high-resolution scanning probe microscopic techniques. The experimental structural analysis performed at the nanoscale, combined with ab initio calculations, allowed us to demonstrate that the molecular architectures we found arise from the simultaneous fulfillment of site adsorption energy maximization driven by peculiar molecular motifs of the selected substrate, close-packing criteria, and epitaxial locking to the substrate surface by weak van der Waals interactions.

Ultrathin porphyrin and tetra-indole covalent organic frameworks for organic electronics applications.

The electronic and charge transport properties of porphyrin and tetra-indole porphyrinoid single layer covalent organic frameworks (COFs) are investigated by means of density functional theory calculations. Ultrathin diacetylene-linked COFs based on oxidized tetra-indole cores are narrow gap 2D semiconductors, featuring a pronounced anisotropic electronic band structure due to the combination of dispersive and flat band characteristics, while registering high room temperature charge carrier mobilities. The capability of bandgap and charge carrier localization tuning via the careful selection of fourfold porphyrin and porphyrinoid cores and twofold articulated linkers is demonstrated, with the majority of systems exhibiting electronic gap values between 1.75 eV and 2.3 eV. Tetra-indoles are also capable of forming stable monolayers via non-articulated core fusing, resulting in 2D morphologies with extended π-conjugation and semi-metallic behavior.

Magnetic mechanism for the biological functioning of hemoglobin

The role of magnetism in the biological functioning of hemoglobin has been debated since its discovery by Pauling and Coryell in 1936. The hemoglobin molecule contains four heme groups each having a porphyrin layer with a Fe ion at the center. Here, we present combined density-functional theory and quantum Monte Carlo calculations for an effective model of Fe in a heme cluster. In comparison with these calculations, we analyze the experimental data on human adult hemoglobin (HbA) from the magnetic susceptibility, Mössbauer and magnetic circular dichroism (MCD) measurements. In both the deoxygenated (deoxy) and the oxygenated (oxy) cases, we show that local magnetic moments develop in the porphyrin layer with antiferromagnetic coupling to the Fe moment. Our calculations reproduce the magnetic susceptibility measurements on deoxy and oxy-HbA. For deoxy-HbA, we show that the anomalous MCD signal in the UV region is an experimental evidence for the presence of antiferromagnetic Fe-porphyrin correlations. The functional properties of hemoglobin such as the binding of O2, the Bohr effect and the cooperativity are explained based on the magnetic correlations. This analysis suggests that magnetism could be involved in the functioning of hemoglobin.

Electrocatalytic Reduction of Oxygen at Glassy Carbon Electrodes Coated with Diazonium‐derived Porphyrin/Metalloporphyrin Films

AbstractIn this study, the influence of the film structure was investigated on the electrocatalytic oxygen reduction at GC electrodes covered with porphyrin and metalloporphyrin rings via the diazonium modification method. For that purpose, primarily, tetraphenylporphyrin (TPP) films on GC electrode surfaces were prepared by electroreduction of in situ generated diazonium salts of 5‐(4‐aminophenyl)‐10,15,20‐triphenylporphyrin (APP) and 5,10,15,20‐tetrakis(4‐aminophenyl)porphyrin (TAPP) molecules. Next, the formation of metalloporphyrin films on the modified surfaces was accomplished through the complexation reactions of surface porphyrin rings with metal ions in the salt solutions containing Mn(II), Fe(III) and Co(II) ions. The resulting porphyrin and metalloporphyrin layers were identified with XPS and ICP‐MS. The electrochemical barrier properties of the films on GC surfaces were examined by cyclic voltammetry in K3Fe(CN)6 aqueous solution. The electrocatalytic abilities of the resulting films were also investigated for the oxygen electrochemical reduction by employing cyclic voltammetry in PBS solutions saturated with oxygen. The results showed that the oxygen reduction potentials on modified GC electrodes were shifted to less negative potentials compared to that of bare GC electrode. Also, it was obtained that the oxygen reduction reaction was more effective on the GC electrodes modified with TPP rings by using TAPP molecules than those prepared by using APP molecules.

Optimization of ZnO Nanorods Growth on Polyetheresulfone Electrospun Mats to Promote Antibacterial Properties.

Zinc oxide (ZnO) nanorods grown by chemical bath deposition (CBD) on the surface of polyetheresulfone (PES) electrospun fibers confer antimicrobial properties to the obtained hybrid inorganic–polymeric PES/ZnO mats. In particular, a decrement of bacteria colony forming units (CFU) is observed for both negative (Escherichia coli) and positive (Staphylococcus aureus and Staphylococcus epidermidis) Grams. Since antimicrobial action is strictly related to the quantity of ZnO present on surface, a CBD process optimization is performed to achieve the best results in terms of coverage uniformity and reproducibility. Scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) provide morphological and compositional analysis of PES/ZnO mats while thermogravimetric analysis (TGA) is useful to assess the best process conditions to guarantee the higher amount of ZnO with respect to PES scaffold. Biocidal action is associated to Zn2+ ion leaching in solution, easily indicated by UV–Vis measurement of metallation of free porphyrin layers deposited on glass.

Vanadyl spin qubit 2D arrays and their integration on superconducting resonators

2D vanadyl porphyrin layers are shown to possess superior spin coherence and to purvey an optimal interface with superconducting circuits.

A Conjugated Copper Porphyrin Polymer for Catalytic Coupling of Acetonitrile and Alcohols

AbstractA nitrogen‐phenyl‐bridged copper porphyrin polymer was synthesized, and copper ions were further coordinated on the bridging imine groups to obtain a copper porphyrin polymer containing two coordinative copper ions (Cu–MP−Cu‐2). The polymer was characterized by IR, SEM/TEM, N2 adsorption and XPS. Cu–MP−Cu‐2 has an unequal columnar structure accumulated by porphyrin layers with diameters of about 20–100 nm. Cu–MP−Cu‐2 also has an excellent micro‐mesoporous structure on the surface and in the interior. Under the synergistic catalysis of imino‐coordinated Cu(II) and Cu(II) in the porphyrin ring, the polymer can catalyze the oxidative coupling of alcohols and acetonitrile to form β‐ketonitrile compounds with high efficiency because of its special structure. The Cu–MP−Cu‐2 remained stable and still had high catalytic activity after several recycles.