58188-48-0

Upstream product

• 109-97-7 pyrrole 
• 3264-82-2 nickel(II) acetylacetonate 
• 1571-08-0 methyl 4-formylbenzoate 
• 3609-53-8 methyl 4-acetylbenzoate 
• 22112-83-0 5,10,15,20-tetrakis(4-methoxycarbonylphenyl)porphyrin 

Downstream Products

• 125824-99-9 Ni-T(p-CO₂CH₃)PPCHO 

Relevant academic research and scientific papers

Thermodynamically Guided Synthesis of Mixed-Linker Zr-MOFs with Enhanced Tunability

Guided by thermodynamics, we have synthesized two mixed-linker zirconium-based metal-organic frameworks (Zr-MOFs), namely, PCN-133 and PCN-134. Both of them possess a layer-pillar structure, in which the connection between Zr6 clusters and primary BTB linkers form a (3,6)-connected kdg layer that is further extended into 3D frameworks by auxiliary DCDPS/TCPP linkers (BTB = benzene tribenzoate, DCDPS = 4,4′-dicarboxydiphenyl sulfone, TCPP = tetrakis(4-carboxyphenyl)porphyrin). PCN-134 demonstrates high porosity (N2 uptake of 717 cm3·g-1 and BET surface area of 1946 cm2·g-1) and excellent chemical stability in aqueous solutions with pH values ranging from 0 to 13. More importantly, PCN-134 tolerates the partial absence of auxiliary linkers leading to structural defects during the assembly process while preserving its framework integrity. Furthermore, the defect density can be systematically controlled by tuning the occupancy of the auxiliary linker, which in turn affects the MOF properties. For instance, the dichromate uptake of PCN-134 is tuned by adjusting the BTB/TCPP ratios, which gives rise to an efficient dichromate absorbent when the TCPP molar ratio in linkers is set as 22%. In addition, the photocatalytic reduction of Cr(VI) in aqueous solution was also performed by PCN-134-22%TCPP which exhibits excellent catalytic activity. This work not only opens up a new synthetic route toward mixed-linker MOFs, but also provides tunable control of MOF defects and, in turn, the properties.

A Ni-2,2′-bisdipyrrinato complex as a potential sensitizer: Synthesis and photoelectrochemical characterization

A novel Ni-based 2,2′-bisdipyrrinato complex bearing peripheral benzoic acid groups (Ni-bisdpmCOOH) has been synthesized and characterized. Electrochemical investigations revealed a high energy LUMO level that, combined with its absorption properties extending up to the NIR region, is compatible with its use as a sensitizer in thermodynamically uphill photocatalytic reactions, such as proton and carbon dioxide photoreduction. A sensitized photo-anode was prepared by adsorbing Ni-bisdpmCOOH onto a TiO2 film, which showed an incident photon to current efficiency, measured at 0.62 V vs. RHE, extending up to the visible light region. This demonstrates that electronically excited Ni-bisdpmCOOH is effectively able to inject electrons into the conduction band of TiO2, thus opening the way for effective TiO2 sensitization or MOF implementation of the molecule itself for energetic applications.

Metallization-Prompted Robust Porphyrin-Based Hydrogen-Bonded Organic Frameworks for Photocatalytic CO2 Reduction

Under topological guidance, the self-assembly process based on a tetratopic porphyrin synthon results in a hydrogen-bonded organic framework (HOF) with the predicted square layers topology (sql) but unsatisfied stability. Strikingly, simply introducing a transition metal in the porphyrin center does not change the network topology but drastically causes noticeable change on noncovalent interaction, orbital overlap, and molecular geometry, therefore ultimately giving rise to a series of metalloporphyrinic HOFs with high surface area, and excellent stability (intact after being soaked in boiling water, concentrated HCl, and heated to 270 °C). On integrating both photosensitizers and catalytic sites into robust backbones, this series of HOFs can effectively catalyze the photoreduction of CO2 to CO, and their catalytic performances greatly depend on the chelated metal species in the porphyrin centers. This work enriches the library of stable functional HOFs and expands their applications in photocatalytic CO2 reduction.

Symmetry-Guided Synthesis of N,N′-Bicarbazole and Porphyrin-Based Mixed-Ligand Metal-Organic Frameworks: Light Harvesting and Energy Transfer

In the past decades, many attempts have been made to mimic the energy transfer (EnT) in photosynthesis, a key process occurring in nature that is of fundamental significance in solar fuels and sustainable energy. Metal-organic frameworks (MOFs), an emerging class of porous crystalline materials self-assembled from organic linkers and metal or metal cluster nodes, offer an ideal platform for the exploration of directional EnT phenomena. However, placing energy donor and acceptor moieties within the same framework with an atomistic precision appears to be a major synthesis challenge. In this work, we report the design and synthesis of a highly porous and photoactive N,N′-bicarbazole- and porphyrin-based mixed-ligand MOF, namely, NPF-500-H2TCPP (NPF = Nebraska porous framework; H2TCPP = meso-tetrakis(4-carboxyphenyl)porphyrin), where the secondary ligand H2TCPP is incorporated precisely through the open metal sites of the equatorial plane of the octahedron cage resulting from the underlying (4,8) connected network of NPF-500. The efficient EnT process from N,N′-bicarbazole to porphyrin in NPF-500-H2TCPP was captured by time-resolved spectroscopy and exemplified by photocatalytic oxidation of thioanisole. These results demonstrate not only the capability of NPF-500 as the scaffold to precisely arrange the donor-acceptor assembly for the EnT process but also the potential to directly utilize the EnT process for photocatalytic applications.

Porphyrin-based NiFe Porous Organic Polymer Catalysts for the Oxygen Evolution Reaction

Porphyrin-based NiFe porous organic polymers (POPs) have been synthesized with good porosity and large BET surface areas (261 to 313 m2 g?1). These bimetallic POPs exhibit RuO2-like OER activity, with the reaction for catalyst FeTAPP-NiTCPP-POP reaching a current density of 10 mA cm?2 at a low overpotential of 338 mV and with a small Tafel slope of 52 mV dec?1. FeTAPP-NiTCPP-POP was stable over a long period under reaction conditions. These bimetallic POPs exhibit better catalytic activity than their monometallic counterparts, due to synergetic interactions between the iron and nickel centers to facilitate the electrocatalytic process.

A series of highly stable porphyrinic metal-organic frameworks based on iron-oxo chain clusters: design, synthesis and biomimetic catalysis

Iron-based porphyrinic metal-organic frameworks (PMOFs) are desirable for biomimetic applications, due to the low toxicity and high abundance of Fe as well as the rich biomimetic functions of metalloporphyrins. Besides, the uniform dispersion of porphyrin centers in PMOFs can effectively protect them from self-dimerization. Nevertheless, it remains a big challenge to synthesize iron-based PMOFs. In this study, a series of Fe-oxo chain-based PMOFs incorporating different metals in porphyrinic centers (namely M-PMOF-3(Fe), M = Fe, Co, Ni, Cu) are synthesized directly from the reaction of metalloporphyrin and iron salts with an improved modulating strategy using a pair of monocarboxylic acids and water as the three-component modulator. The prepared materials of M-PMOF-3(Fe) possess high stability to resist a broad pH range (0-11) and even 2 M HCl in aqueous solutions for 2 days, and their frameworks can be maintained up to 350 °C. Catalytic tests show that M-PMOF-3(Fe) are effective in the aerobic oxidation of C-H bonds using oxygen from the air as the oxidant.

Boosting Interfacial Charge-Transfer Kinetics for Efficient Overall CO2Photoreduction via Rational Design of Coordination Spheres on Metal-Organic Frameworks

The recombination of electron-hole pairs severely detracts from the efficiency of photocatalysts. This issue could be addressed in metal-organic frameworks (MOFs) through optimization of the charge-transfer kinetics via rational design of structures at atomic level. Herein, a pyrazolyl porphyrinic Ni-MOF (PCN-601), integrating light harvesters, active catalytic sites, and high surface areas, has been demonstrated as a superior and durable photocatalyst for visible-light-driven overall CO2 reduction with H2O vapor at room temperature. Kinetic studies reveal that the robust coordination spheres of pyrazolyl groups and Ni-oxo clusters endow PCN-601 with proper energy band alignment and ultrafast ligand-to-node electron transfer. Consequently, the CO2-to-CH4 production rate of PCN-601 far exceeds those of the analogous MOFs based on carboxylate porphyrin and the classic Pt/CdS photocatalyst by more than 3- and 20-fold, respectively. The reaction avoids the use of hole scavengers and proceeds in a gaseous phase which can take full advantage of the high gas uptake of MOFs. This work demonstrates that the rational design of coordination spheres in MOF structures not only reconciles the contradiction between reactivity and stability but also greatly promotes the interfacial charge transfer to achieve optimized kinetics, providing guidance for the design of highly efficient MOF photocatalysts.

Visible-Light-Assisted Photocatalytic Reduction of Nitroaromatics by Recyclable Ni(II)-Porphyrin Metal-Organic Framework (MOF) at RT

A microporous Ni(II)-porphyrin metal-organic framework (MOF), [Ni3(Ni-HTCPP)2(μ2-H2O)2(H2O)4(DMF)2]·2DMF, (MOF1) (where, Ni-HTCPP = 5,10,15,20-tetrakis(4-benzoate) porphyrinato-Ni(II)) has been synthesized by the solvothermal route. Single-crystal X-ray diffraction study of 1 reveals a 2D network structure constituted by Ni3 cluster and [Ni-HTCPP]3- metalloligand having (3, 6)-connected binodal net with {43}2{46·66·83}-kgd net topology. The 2D layers are further stacked together through π-π interactions between the porphyrin linkers to generate a 3D supramolecular framework which houses 1D channels with dimension of ～5.0 × 9.0 ?2 running along the crystallographic a-axis. Visible-light-assisted photocatalytic investigation of MOF1 for heterogeneous reduction of various nitroaromatics at room temperature resulted in the corresponding amines with high yield and selectivity. On the contrary, the Ni(II)-centered porphyrin tetracarboxylic acid [Ni-H4TCPP] metalloligand does not show the photocatalytic activity under similar conditions. The remarkably high catalytic performance of MOF1 over [Ni-H4TCPP] metalloligand has been attributed due to cooperative catalysis involving the Ni-centered porphyrin secendary building units (SBUs) and the Ni3-oxo node. Further, the MOF1 was recycled and reused up to three cycles without any significant loss of catalytic activity as well as structural rigidity. To the best of our knowledge, MOF1 represents the first example of MOF based on 3d metal ion exhibiting visible-light-assisted reduction of nitroaromatics under mild conditions without the assistance of noble metal cocatalysts.

Construction of ultrastable porphyrin Zr metal-organic frameworks through linker elimination

A series of highly stable MOFs with 3-D nanochannels, namely PCN-224 (no metal, Ni, Co, Fe), have been assembled with six-connected Zr6 cluster and metalloporphyrins by a linker-elimination strategy. The PCN-224 series not only exhibits the highest BET surface area (2600m2/g) among all the reported porphyrinic MOFs but also remains intact in pH = 0 to pH = 11 aqueous solution. Remarkably, PCN-224(Co) exhibits high catalytic activity for the CO2/propylene oxide coupling reaction and can be used as a recoverable heterogeneous catalyst.

Synthesis of calix[3]dipyrrins by a modified Lindsey protocol

(Figure Presented) Bowled over: Calix[3]dipyrrins were synthesized from pyrrole and aryl aldehyde precursors by the Lindsey protocol, modified by the presence of a small amount of water. These bowl-shaped macrocycles can accommodate three metal (M) ions such as NiII and CuII in a hexagonal M3O3 manner (see structure; Cu green, N blue, O red, C black).