Porphyrin Research Articles

Three-dimensional Covalent Organic Framework with Dense Lithiophilic Sites as Protective Layer to Enable High-Performance Lithium Metal Battery.

Lithium (Li) metal batteries with remarkable energy densities are restrained by short lifetime and low Coulombic efficiency (CE), resulting from the accumulative Li dendrites and dead Li during cycling. Here, we prepared a new three-dimensional (3D) covalent organic framework (COF) with dense lithiophilic sites (heteoatom weight contents of 32.32wt%) as an anodic protective layer of Li metal batteries. The 3D COF was synthesized using a [6+4] synthesis strategy by inducing flexible 6-connected cyclotriphosphazene derivative aldehyde and 4-connected porphyrin-based tetraphenylamines. Both phosphazene and porphyrin rings in the COF served as electron-rich and lithiophilic sites, enhancing a homogeneous Li+ flux via 3D direction towards highly smooth and compact Li deposition. The Li/Por-PN-COF-Cu cells achieved a record average CE of 99.1% for 320 cycles with smooth Li deposition. Meanwhile, the abundant lithiophilic sites can promote fast Li+ transport with Li+ transference number of 0.87, enabling LiFePO4 full cell with stable stripping/plating processes even at a harsh rate of 5 C. Theoretical calculations revealed that the strong interaction force between Li+ and the COF facilitated the dissolution of Li+ from the electrolyte, and the low migration barrier of 1.08 eV indicated a favorable interaction between the Li+ ions and the π-electron system.

Three‐dimensional Covalent Organic Framework with Dense Lithiophilic Sites as Protective Layer to Enable High‐Performance Lithium Metal Battery

Lithium (Li) metal batteries with remarkable energy densities are restrained by short lifetime and low Coulombic efficiency (CE), resulting from the accumulative Li dendrites and dead Li during cycling. Here, we prepared a new three‐dimensional (3D) covalent organic framework (COF) with dense lithiophilic sites (heteoatom weight contents of 32.32wt%) as an anodic protective layer of Li metal batteries. The 3D COF was synthesized using a [6+4] synthesis strategy by inducing flexible 6‐connected cyclotriphosphazene derivative aldehyde and 4‐connected porphyrin‐based tetraphenylamines. Both phosphazene and porphyrin rings in the COF served as electron‐rich and lithiophilic sites, enhancing a homogeneous Li+ flux via 3D direction towards highly smooth and compact Li deposition. The Li/Por‐PN‐COF‐Cu cells achieved a record average CE of 99.1% for 320 cycles with smooth Li deposition. Meanwhile, the abundant lithiophilic sites can promote fast Li+ transport with Li+ transference number of 0.87, enabling LiFePO4 full cell with stable stripping/plating processes even at a harsh rate of 5 C. Theoretical calculations revealed that the strong interaction force between Li+ and the COF facilitated the dissolution of Li+ from the electrolyte, and the low migration barrier of 1.08 eV indicated a favorable interaction between the Li+ ions and the π‐electron system.

Highly efficient solar steam evaporation via elastic polymer covalent organic frameworks monolith

Three-dimensional solar steam evaporators with efficient water purification performance have received increasing attention recently. Herein, elastic polymer covalent organic frameworks (PP-PEG) containing PEG chains with intriguing adaptability to guests are prepared by forming porphyrin rings. PP-PEG foams demonstrate full spectrum absorbance and excellent photothermal conversion properties. Through well-designed thermal management and optimization of the hydrophilicity and PEG chain length, we obtain a highly efficient solar evaporator with an evaporation rate of 4.89 kg m−2 h−1 under 1 sun in self-contained mode. The optimized solar evaporation rate is increased to 18.88 kg m−2 h−1 under 1 sun with a facile truncated cone reflector, exceeding all known solar steam evaporators. This innovative design holds immense promise for desalination and water purification owing to its simple preparation, high efficiency and durability.

Supramolecular Catalyst for Improving the Sensitivity of Biomolecule Detection

AbstractSupermolecule refers to two or more molecules that are bonded together by secondary bonds between molecules to form a multimolecular system at the level of more than molecules. At this point, the molecules form an orderly aggregation, showing its unique structure and function. Supramolecular catalysts can form structures with specific functions through non‐covalent interactions (e. g., hydrogen bonding, π‐π stacking, etc.) to mimic the catalytic mechanism of natural enzymes and achieve susceptible and specific detection of biomolecules. The application of supramolecules is mainly focused on the self‐assembly of components for the construction of sensing platform. Therefore, supramolecular catalysts have a huge potential in biomolecule detection. This article focuses on the application of cyclodextrins(CD), cucurbit[n]uril(CB), porphyrins(PP) and Calix[n]arenes(CA) in the field of catalysis and in improving detection sensitivity. Research progress of supramolecular catalysts in polymerization amplification is summarized in this paper.

Application and Challenge of Metalloporphyrin Sensitizers in Noninvasive Dynamic Tumor Therapy

Dynamic tumor therapies (mainly including photodynamic therapy (PDT) and sonodynamic therapy (SDT)) offer new approaches to cancer treatment. They are often characterized by their noninvasive nature, high selectivity, and low toxicity. Sensitizers are crucial for dynamic therapy. Developing efficient sensitizers with good biocompatibility and controllability is an important aim in dynamic therapy. Porphyrins and metalloporphyrins attract great attention due to their excellent photophysical properties and low cytotoxicity under non-light. Compared to porphyrins, metalloporphyrins show greater potential for dynamic therapy due to their enhanced photochemical and photophysical properties after metal ions coordinate with porphyrin rings. This paper reviews some metalloporphyrin-based sensitizers used in photo/sonodynamic therapy and combined therapy. In addition, the probable challenges and bottlenecks in clinical translation are also discussed.

Boosting photothermal conversion through array aggregation of metalloporphyrins in bismuth-based coordination frameworks.

Materials capable of efficiently converting near-infrared (NIR) light into heat are highly sought after in biotechnology. In this study, two new three-dimensional (3D) porphyrin-based metal-organic frameworks (MOFs) with a sra-net, viz. CoTCPP-Bi/NiTCPP-Bi, were successfully synthesized. These MOFs feature bismuth carboxylate nodes interconnected by metalloporphyrinic spacers, forming one-dimensional (1D) arrays of closely spaced metalloporphyrins. Notably, the CoTCPP-Bi exhibits an approximate Co⋯C distance of 3 Å, leading to enhanced absorption of NIR light up to 1400 nm due to the presence of strong interlayer van der Waals forces. Furthermore, the spatial arrangement of the metalloporphyrins prevents axial coordination at the centers of porphyrin rings and stabilizes a CoII-based metalloradical. These characteristics promote NIR light absorption and non-radiative decay, thereby improving photothermal conversion efficiency. Consequently, CoTCPP-Bi can rapidly elevate the temperature from room temperature to 190 °C within 30 seconds under 0.7 W cm-2 energy power from 808 nm laser irradiation. Moreover, it enables solar-driven water evaporation with an efficiency of 98.5% and a rate of 1.43 kg m-2 h-1 under 1 sun irradiation. This research provides valuable insights into the strategic design of efficient photothermal materials for effective NIR light absorption, leveraging the principles of aggregation effect and metalloradical chemistry.

Plasma and urinary CP I and CP III concentrations in chimeric mice with human hepatocytes after rifampicin administration.

The interest in transporter-mediated drug interactions has been increasing in the field of drug development. In this study, we measured the plasma and urinary concentrations of coproporphyrin (CP) I and CP III as endogenous substrates for organic anion-transporting polypeptide (OATP) using chimeric mice with human hepatocytes (PXB mice) and examined the influence of an OATP inhibitor, rifampicin (RIF). CP I and CP III were actively taken up intracellularly, and RIF inhibited the uptake in a concentration-dependent manner for both CP I and CP III in human hepatocytes (PXB-cells). Single doses of RIF at 10 and 30 mg/kg were orally or intravenously administered to PXB mice and wild-type ICR mice. Plasma concentrations (AUC0-8h) of CP I increased in both mice. However, a marked increase in CP III was only observed in ICR mice, after intravenous administration of RIF at 30 mg/kg. The IC50 values of RIF for intracellular CP I/III uptake and the unbound plasma concentrations of RIF suggested that the increase in plasma CP I is associated with the exposure of RIF to OATPs. The 24-h cumulative urinary excretions of CP I and CP III increased in both mice, but more markedly in PXB mice. Thus, RIF increased the plasma and urinary concentrations of CP I and CP III in the mice, as reported in humans, and CP I may be a more sensitive biomarker of OATP-mediated drug interactions in PXB mice.

Repurposing discarded porphyrin waste as electrocatalysts for the oxygen reduction reaction

The oxygen reduction reaction (ORR), presently known as the key bottleneck in the mass-scale implementation of fuel cells (FCs), typically relies on the exploitation of scarce and expensive platinum group metals (PGMs). Meanwhile, as a substitute for PGMs, transition metal-nitrogen carbons (TM-Nx-C) are proving to be reliable electrocatalysts (ECs) in which atomically dispersed TMs coordinated with nitrogen are integrated into the carbon matrix. Such TM-Nx coordination already exists in metal-porphyrins making them suitable precursors for TM-Nx-C. Adler-Longo method is the standard recipe for meso‑tetraphenyl porphyrin realizes ca. 20 % yield whereas the residual polypyrromethenes, structurally resembling open porphyrin rings, are often wasted. Herein, the possibility of upcycling waste polypyrromethenes into efficient TM-Nx-C for ORR is demonstrated. A comprehensive structural and morphological characterization is provided, and the electrocatalytic activity towards ORR in an alkaline environment is discussed using Fe and Mn as TMs. The EC synthesized from pure porphyrin precursor at 600 °C (FeTPP_600) had the best performance recording 0.972 and 0.852 V vs RHE for Eonset and E1/2. Mixing porphyrins with their synthetic waste (ratio of 1:4) and pyrolyzing it at 800 °C (FeTPP/Waste(1:4)_800) still exhibits appreciable kinetics with similar results (0.977 and 0.853 V vs RHE for Eonset and E1/2).

Intramolecular Charge Transfer and Spin-Orbit Coupled Intersystem Crossing in Hypervalent Phosphorus(V) and Antimony(V) Porphyrin Black Dyes.

Porphyrin dyes with strong push-pull type intramolecular charge transfer (ICT) character and broad absorption across the visible spectrum are reported. This combination of properties has been achieved by functionalizing the periphery of hypervalent and highly electron-deficient phosphorus(V) and antimony(V) centered porphyrins with electron-rich triphenylamine (TPA) groups. As a result of the large difference in electronegativity between the porphyrin ring and the peripheral groups, their absorption profiles show several strong charge transfer transitions, which in addition to the porphyrin-centered π → π* transitions, make them panchromatic black dyes with high absorption coefficients between 200 and 800 nm. Time-resolved optical and electron paramagnetic resonance (EPR) studies show that the lowest triplet state also has ICT character and is populated by spin-orbit coupled intersystem crossing.

Understanding the Adsorption and Diffusion Behaviors of PBUT in Biocompatible MOFs.

With the increasing incidence of chronic kidney disease, the effective control of protein-bound uremic toxins (PBUTs), which are difficult to remove through dialysis, has become a priority. In this study, the adsorption and diffusion behaviors of several metal-organic frameworks (MOFs) for PBUTs (indoxyl sulfate and p-cresyl sulfate) were studied by molecular dynamics (MD) simulations and umbrella sampling. For the NU series of MOFs, good correlations between the Gibbs free energy (ΔG) and the experimental clearance rates of PBUTs are found. For the adsorption behaviors, in terms of ΔG, DAJWET exhibits the best adsorption effect for indoxyl sulfate (IS), whereas NU-1000 shows the best effect for p-cresyl sulfate (pCS). Similar trends observed in the radial distribution function and mean square displacement results suggest that the π-π stacking interactions play a crucial role in the adsorption and diffusion of PBUTs by MOFs. Furthermore, it can be concluded that MOFs with highly conjugated groups (porphyrin rings and pyrene groups) tend to generate more PBUT attraction, and provide design principles for potential MOF candidates in the removal of PBUTs.

Exploring novel porphyrin photocatalyst for the conversion of frying oil to biodiesel: A step for globular economy

The current protocol addresses the outcomes on the photo-transesterification of frying sunflower oil (FSO) catalysed by porphyrin comprising sulphonic acid functionalized pyridinium ionic liquid (PcSAFPyIL). A novel photocatalyst was synthesized and confirmed by 1H and 13C NMR, Powder XRD, FT-IR, XPS, and fluorescence emission spectrophotometry. The energy band gap (1.85 eV) was determined by cyclic voltammetry, Hammett acidity (H0 = 0.217) by UV–visible spectrophotometer and metal free nature by powder XRD and XPS. The photocatalytic activity of PcSAFPyIL in the visible region was confirmed by reflecting intense Soret band (421 nm) and four Q bands (515, 554, 591 and 647 nm). This may be due to inherent aromatic characters and conjugation with chromophore groups at meso-position of porphyrin ring. The obtained photocatalyst was scrutinized for the photo-transesterification of FSO in a lab-made photoreactor. The ideal reaction parameters were found to be 20 mg photocatalyst quantity with 1:12 (FSO: ROH) under exposure of 2 x 5 W LED at room temperature, to afford 90 % biodiesel in 24 h. Moreover, the formation of biodiesel was confirmed by (1H, 13C) NMR, FT-IR, DEPT-135, and GC–MS. Further, stability, heterogeneous nature and the gram scale reaction PcSAFPyIL was also efficiently accomplished using the optimized photocatalytic conditions. Additionally, the physicochemical properties of the biodiesel fuel B15 (15 % blended with marketed diesel) and pure marketed diesel are consistent. Moreover, the engine performance and emission characteristics of B15 such as brake-specific fuel consumption (BSFC), break thermal efficiency (BTE) found comparable and better than commercial diesel.

Interfacial modulation strategy using poly(3,4-ethylenedioxythiophene)–poly(4-styrenesulfonate) (PEDOT:PSS) and ultrathin two-dimensional metal–organic framework nanosheets for wearable supercapacitors: Solution engineering

Two-dimensional metal–organic frameworks (2D MOFs) hold great promise as electrochemically active materials. However, their application in MOF nanocomposite electrodes in solution engineering is limited by structural self-stacking and imperfect conductive pathways. In this study, we used meso-tetra(4-carboxyphenyl) porphine (TCPP) with off-domain π-bonds to reconstitute Zn-TCPP (ZMOF) and poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) through an interfacial modulation strategy involving electrostatic coupling and hydrogen bonding, creating a conductive composite with a nanosheet structure. The negatively charged PSS and ZMOF formed a three-dimensional interconnected conductive network with excellent interfaces. The positively charged PEDOT, fine tuned with the lamellar structure, established strong π-π stacking interactions between the porphyrin and thiophene rings. ZMOF also induced changes in the PEDOT chain structure, weakening PSS entanglement and enhancing charge-transport properties. The specific capacitance of the prepared supercapacitor was as high as 967.8 F g−1. Flexible supercapacitors produced on a large scale using dispensing printing technology exhibited an energy density of 1.85 μWh cm−2 and a power density of 7.08 μW cm−2. This interfacial modulation strategy also exhibited excellent wearable properties, with 96 % capacitance retention at a 180° bending angle and stable cycling performance. This study presented a significant advancement in the functionalization of 2D materials, highlighting their potential for device-grade capacitive architectures.

Synthesis, Electrochemistry and Photochemistry of Hypervalent Phosphorus(V) Porphyrin and Antimony(V) Porphyrin Black Dyes

In the last few years, our focus has been on push-pull type hypervalent Group 15 porphyrins with intramolecular charge transfer (ICT) properties. Insertion of P(V) or Sb(V) ion in the porphyrin cavity results in a highly electron-deficient porphyrin center, under this condition the presence of electron-rich units in porphyrin meso-positions results in charge transfer within the molecules. Recently, we extended this strategy to 5,10,5,20-tetrakis(triphenylamine)porphyrin derivative where strong electron donor triphenylamine (TPA) units are in meso-positions. Upon insertion of the P(+5) and Sb(+5) ion, the resulting hypervalent Group 15 porphyrins manifested a strong ICT from the TPA units to the central porphyrin ring. The existence of ICT makes the absorption profiles cover the entire visible region with high molar extinction coefficients. Due to this reason, the studied hypervalent Group 15 porphyrins appear as black dyes. Here, I will present these porphyrins and discuss their structural, redox, and remarkable photophysical properties. Figure 1

Semiconductor Effect from Pd(II) Porphyrin Metal to Its Ligand in Photocatalytic N-Dealkylation.

In this work, four saddled Pd(II) porphyrins were developed as photocatalyst for N-dealkylation of triethyl Rhodamine (TER) under visible light, and their catalytic ability was found to be negatively related to the out-of-plane of their macrocycles. Two important relationships involving the metalloporphyrins as catalyst were revealed: (1) a photoexcitative semiconductor effect between the 4dx 2-γ 2(Pd) and a2u(π) orbitals of Pd(II) porphyrin on the dealkylation. (2) a domino process from strap length, ring geometry, core deformation, d-π gap variation, to photocatalytic activity. Two revelations imply a unidirectional electron transfer route from axial ligand, to central metal, to porphyrin ring based on photoexcitation and guide the design and development of complex photocatalysts, and their revelation is attributed to the acquisition of a series of Pd(II) porphyrins with continuous ring distortion. The findings help to understand the photocatalytic single electron transfer (SET)-first mechanism based on metallic complex.

Influence of subphase temperature on Langmuir layers and thin films of A3B-type porphyrine derivative

The influence of aqueous subphase temperature on the formation and stability of floating layers of 5-(4-hydroxyphenyl)-10,15,20-tris(4-hexadecyloxyphenyl)porphyrin (P-OH) was investigated using the Langmuir technology. It was found that the increase in the subphase temperature from 1 to 40 °C leads to a loosening of floating layers (an increase in the area per molecule in the floating layer by ∼15% and a decrease in the surface compression modulus by more than two times). The stability of floating layers (i.e., the ability of a floating layer to maintain its area under the action of a constant compressive force) decreases with increasing subphase temperature. It has been shown that the most stable floating layers are formed at subphase temperatures lower than 30 °C. Monolayer films on solid substrates were obtained using the Langmuir-Schafer technique at subphase temperatures of 1, 10, 20, 30, and 40 °C. The surface relief of these films was studied by atomic force microscopy (AFM). The AFM analysis revealed that the films transferred from the aqueous subphase at a temperature of 20 °C had the highest continuity and the lowest roughness. The absorption spectra of the floating layers were obtained, in which a bathochromic shift of the Soret band and Q-bands were registered (by 19 nm at 20 °C) in comparison with chloroform solution spectrum. This shift is a consequence of the strong intermolecular π–π* interaction, resulting in the formation of J-type aggregates. The Soret band in the spectra of the floating layers shifted from 436 to 441 nm with an increase in subphase temperature from 1 to 40 °C. In the absorption spectra of thin films (8 transfers), the indicated shifts of absorption bands as well as a broadening of the Soret band are preserved. The results of this work can be used in the targeted creation of film samples with specific structure and properties.

Optical properties of meso-tetra(sulphonatophenyl) porphyrins (TPPS 4) and their Fe 3+, Mn 3+, Zn 2+ complexes with different pH values studied using by picosecond pulse trains

Applying picosecond pulse trains propagating in meso-tetra(sulphonatophenyl) porphyrins and their Fe 3+, Mn 3+, Zn 2+ complexes, we studied the nonlinear dynamics at different pH values. The pulse train at wavelength 532nm is comprised of 20 subpulses with 70ps width and 13ns spacing. We simplified the energy structures of porphyrins and metalloporphyrins to five-level models. In solving coupled rate equations and two-dimensional paraxial field, we used Crank-Nicholson numerical method to do the calculations. The results revealed that in irregular metalloporphyrins with central paramagnetic ion Mn 3+ or Fe 3+, the central ion would act as electron acceptor, which leads to charge transfer of unpaired metal electron to the porphyrin ring π conjugated system, and strengthen the spin–orbit coupling of electronic systems and weaken the transition prohibition between electronic states in porphyrins. However regular metalloporphyrins with central diamagnetic ion Zn 2+ has similar optical properties to free base porphyrins, and Zn 2+ TPPS 4 has much longer excited state lifetimes and slower intersystem crossing. In solutions, hydrogen bond would be formed to porphyrin, which can change the transitions of π electrons and thus the charge transfer can be strengthened in the porphyrin ring. In weak intensity region with linear absorption, nonprotonated porphyrins with high pH value show better optical limiting (OL) effect. Conversely in high intensity region, protonated porphyrins with low pH value show better OL effect. Besides, increasing interaction distances of porphyrins and metalloporphyrins with laser pulses is another important factor to raise the OL effects.

Effect of CO binding to P450 BM3 F393 mutants on electron density distribution in the heme cofactor

Resonance Raman spectroscopy has been performed on a set of cytochrome P450 BM3 heme domains in which mutation of the highly conserved Phe393 induces significant variation in heme iron reduction potential. In previous work [Chen, Z., Ost, T.W.B., and Schelvis, J.P.M. (2004) Biochemistry 43, 1798–1808], a correlation between heme vinyl conformation and the heme iron reduction potential indicated a steric control by the protein over the distribution of electron density in the reduced heme cofactor. The current study aims to monitor changes in electron density on the ferrous heme cofactor following CO binding. In addition, ferric-NO complexes have been studied to investigate potential changes to the proximal Cys400 thiolate. We find that binding of CO to the ferrous heme domains results in a reorientation of the vinyl groups to a largely out-of-plane conformation, the extent of which correlates with the size of the residue at position 393. We conclude that FeII dπ back bonding to the CO ligand largely takes away the need for conjugation of the vinyl groups with the porphyrin ring to accommodate FeII dπ back bonding to the porphyrin ligand. The ferrous-CO and ferric-NO data are consistent with a small decrease in σ-electron donation from the proximal Cys400 thiolate in the F393A mutant and, to a lesser extent, the F393H mutant, potentially due to a small increase in hydrogen bonding to the proximal ligand. Phe393 seems strategically placed to preserve robust σ-electron donation to the heme iron and to fine-tune its electron density by limiting vinyl group rotation.

Obscurity of chlorophyll tails - Is chlorophyll with farnesyl tail incorporated into PSII complexes?

Chlorophyll is essential in photosynthesis, converting sunlight into chemical energy in plants, algae, and certain bacteria. Its structure, featuring a porphyrin ring enclosing a central magnesium ion, varies in forms like chlorophyll a, b, c, d, and f, allowing light absorption at a broader spectrum. With a 20-carbon phytyl tail (except for chlorophyll c), chlorophyll is anchored to proteins. Previous findings suggested the presence of chlorophyll with a modified farnesyl tail in thermophilic cyanobacteria Thermosynechoccocus vestitus. In our Arabidopsis thaliana PSII cryo-EM map, specific chlorophylls showed incomplete phytyl tails, suggesting potential farnesyl modifications. However, further high-resolution mass spectrometry (HRMS) analysis in A. thaliana and T. vestitus did not confirm the presence of any farnesyl tails. Instead, we propose the truncated tails in PSII models may result from binding pocket flexibility rather than actual modifications.

Expanding Role of Endogenous Biomarkers for Assessment of Transporter Activity in Drug Development: Current Applications and Future Horizon.

The evaluation of transporter-mediated drug-drug interactions (DDIs) during drug development and post-approval contributes to benefit-risk assessment and helps formulate clinical management strategies. The use of endogenous biomarkers, which are substrates of clinically relevant uptake and efflux transporters, to assess the transporter inhibitory potential of a drug has received widespread attention. Endogenous biomarkers, such as coproporphyrin (CP) I and III, have increased mechanistic understanding of complex DDIs. Other endogenous biomarkers are under evaluation, including, but not limited to, sulfated bile acids and 4-pyridoxic acid (PDA). The role of endogenous biomarkers has expanded beyond facilitating assessment of transporter-mediated DDIs and they have also been used to understand alterations in transporter activity in the setting of organ dysfunction and various disease states. We envision that endogenous biomarker-informed approaches will not only help to formulate a prudent and informed DDI assessment strategy but also facilitate quantitative predictions of changes in drug exposures in specific populations.

Hydrogen‐Bond‐Enhanced Photoreforming of Biomass Furans over a Urea‐Incorporated Cu(II) Porphyrin Framework

AbstractSolar‐driven upgrading of biomass‐derived 5‐hydroxylmethylfurfural (HMF) to 2,5‐furandicarboxylic acid (FDCA) holds great promise for sustainable production of bio‐plastics and resins. However, the process is limited by poor selectivity and sluggish kinetics due to the vertical coordination of HMF at relatively strong metal sites. Here, we purposely developed a Cu(II) porphyrin framework featuring side‐chain incorporated urea linkages, denoted as TBUPP−Cu MOF, to render HMF a weak hydrogen bond at the urea site and flat adsorption via π–π stacking with the benzene moiety. The unique configuration promotes the approaching of −CHO of HMF to the photoexcited porphyrin ring towards kinetically and thermodynamically favourable intermediate formation and subsequent desorption. The charge localisation and orbital energy alignment enable the selective activation of O2 over the porphyrin to generate ⋅O2− and 1O2 instead of highly oxidative H2O2 and ⋅OH via spin‐flip electron transfer, which drive the ambient oxidation of proximal −CHO. The effective utilisation of redox species and circumvented over‐oxidation facilitate a FDCA selectivity of >90 % with a high turnover number of 193 molHMF molCu−1. The facile purification of high‐purity FDCA and zero‐waste recycling of intermediates and durable catalyst feature TBUPP−Cu MOF a promising photo‐oxidation platform towards net‐zero biorefining and organic transformations.