Porphyrin-based Porous Organic Polymer Research Articles

A ruthenium porphyrin-based porous organic polymer for the hydrosilylative reduction of CO2 to formate.

A ruthenium porphyrin-based porous organic polymer (POP) was synthesized, characterized, and used to reduce CO2 to a formate salt. We demonstrate that Ru-BBT-POP can be utilized to reduce CO2 to a silyl formate and then converted to potassium formate with a respectable turnover number and frequency.

A porphyrin porous organic polymer with bicatalytic sites for highly efficient one-pot tandem catalysis.

A novel porphyrin-based porous organic polymer PPOP-1(Pd) with bifunctional catalytic sites was constructed via imine condensation of tetra(4-aminophenyl)porphyrin and acenaphthenequinone. PPOP-1(Pd) containing Pd(ii)-porphyrin and Pd(ii)-α-diimine moieties exhibits excellent catalytic activity and outstanding reusability for tandem catalytic reactions of C-H arylation and Suzuki coupling.

Facile one-pot synthesis of a porphyrin-based hydrophilic porous organic polymer and application as recyclable absorbent for selective separation of methylene blue

With the development of dye production and printing industry, dyes wastewater has increased dramatically. The resulting environmental pollution problem is increasing seriously. In the present work, a porphyrin-based porous organic polymer (PPOPs-OH) was synthesized by using pyrrole and 2,6-dihydroxynaphthalene-1,5-dicarbaldehyde (DHNDA) as basic building block in situ. This method was cost- and time-efficient, without the participation of metal catalysts. Further reaction of PPOPs-OH with chlorosulfonic acid, a new sulfonic acid functional material (PPOPs-SO3H) was obtained with the increasing electronegativity and hydrophilicity. PPOPs-SO3H exhibit good adsorption capacity for methylene blue (MB) from water (980.4 mg g−1) and excellent selectivity for MB in the present of rhodamine B (RhB) and methyl orange (MO). Mechanism investigation revealed that electrostatic in comparison with π-π interaction is the prominent force in the absorption process. Recycling experiments found the absorption properties of PPOPs-SO3H did not reduce significantly after several cycles. As a consequence, our findings highlight an appealing opportunities for covalent organic polymers with their potential application as high-efficiency and robust adsorbents for pollutants removal and environmental protection.

Porphyrin based porous organic polymer modified with Fe3O4 nanoparticles as an efficient adsorbent for the enrichment of benzoylurea insecticides.

Porphyrin-based porous organic polymers (P-POPs) are amorphous polymers linked by strong covalent bonds between the porphyrin subunits that act as building blocks. The authors describe a magnetic P-POP that possesses high surface area, a highly porous structure, and strong magnetism. The MP-POP was employed as a magnetic sorbent for the extraction of benzoylurea insecticides from cucumber and tomato samples prior to their determination by HPLC. The sorbent has a typical sorption capacity of 1.90-2.00mg∙g-1. The method exhibits a good linear range (0.8-160ng·g-1), low limits of detection (0.08-0.2ng·g-1), and high method recoveries (81.8-103.5%) for cucumber and tomato samples. The MP-POP has different adsorption capabilities for the benzoylurea insecticides, phenylurea herbicides and phenols compounds, and the adsorption mechanism is found to be based on π-stacking, hydrogen-bonding, and hydrophobic interactions. Graphical abstract A novel magnetic porphyrin-based porous organic polymer was fabricated and used as the adsorbent for the efficient extraction of benzoylurea insecticides.

Preparation of a magnetic porous organic polymer for the efficient extraction of phenylurea herbicides

A magnetic porphyrin-based porous organic polymer (M-PPOP) with good porosity, high surface area and strong magnetism was prepared and employed as the adsorbent for the magnetic solid phase extraction of the phenylurea herbicides (metoxuron, monolinuron, chlorotoluron, and buturon) from bottled grape juice and tomato samples prior to their determination by high performance liquid chromatography. Under the optimized conditions, the developed method exhibited a good linear range, low limits of detection, low relative standard deviations (<6.8%), good method recoveries between 80.8% and 117%, and high enrichment factors (51–106). For a better elucidation of the adsorption of the M-PPOP towards the analytes, the extraction performance of the M-PPOP for different types of organic compounds including polycyclic aromatic hydrocarbons, phenylurea insecticides, phenylurea herbicides and phenols was studied. The results indicated that the π- stacking, hydrogen-bonding and hydrophobic interactions between the M-PPOP and the analytes played a main role for the adsorption. The results revealed that the M-PPOP material had a great potential for the enrichment of more organic pollutants from real samples.

A three-dimensional porphyrin-based porous organic polymer with excellent biomimetic catalytic performance

A porphyrin-based porous organic polymer PPOP-1(Fe) with a three-dimensional diamond structure was synthesized, which exhibits high stability and excellent catalytic efficiency as a biomimetic catalyst.

A Hexagonal Covalent Porphyrin Framework as an Efficient Support for Gold Nanoparticles toward Catalytic Reduction of 4-Nitrophenol.

A hexagonal porphyrin-based porous organic polymer, namely, CPF-1, was constructed by 3+2 ketoenamine condensation of the C2 -symmetric porphyrin diamine 5,15-bis(4-aminophenyl)-10,20-diphenylporphyrin and 1,3,5-triformylphloroglucinol. This material exhibits permanent porosity and excellent thermal and chemical stability. CPF-1 can be employed as a superior supporting substrate to immobilize Au nanoparticles (NPs) as a result of the strong interactions between Au NPs and the CPF support. An Au@CPF-1 hybrid was synthesized by an interfacial solution infiltration method with NaBH4 as reducing agent. Au NPs (5 nm) grew on CPF-1 and were distributed without aggregation. Moreover, Au@CPF-1 exhibits superior catalytic activity compared to many other reported Au-based catalysts for the reduction of 4-nitrophenol in the presence of NaBH4 . In addition, Au@CPF-1 has excellent stability and recyclability, and it can be reused for three successive reaction cycles without loss of activity. The dense distribution of phenyl rings on the channel walls of the CPF support can reasonably be regarded as the active sites that adsorb the 4-nitrophenol molecule through hydrogen-bonding and C-H⋅⋅⋅π interactions, as was confirmed by the X-ray structure of model compound DAPP-Benz.

Stable and catalytically active iron porphyrin-based porous organic polymer: Activity as both a redox and Lewis acid catalyst.

A new porphyrin-based porous organic polymer (POP) with BET surface area ranging from 780 to 880 m2/g was synthesized in free-base form via the reaction of meso-tetrakis(pentafluorophenyl) porphyrin and a rigid trigonal building block, hexahydroxytriphenylene. The material was then metallated with Fe(III) imparting activity for Lewis acid catalysis (regioselective methanolysis ring-opening of styrene oxide), oxidative cyclization catalysis (conversion of bis(2-hydroxy-1-naphthyl)methanes to the corresponding spirodienone), and a tandem catalytic processes: an in situ oxidation-cyclic aminal formation-oxidation sequence, which selectively converts benzyl alcohol to 2-phenyl-quinazolin-4(3H)-one. Notably, the catalyst is readily recoverable and reusable, with little loss in catalytic activity.

A triazine functionalized porous organic polymer: excellent CO2storage material and support for designing Pd nanocatalyst for C–C cross-coupling reactions

One-pot bottom-up synthesis involving extended aromatic electrophilic substitution on to a pyrrole has been employed for the design of a novel triazine-functionalized porphyrin-based porous organic polymer, TPOP-1. Hydrothermal treatment of 4,4′,4′′-(1,3,5-triazine-2,4,6-triyl)tris(oxy)tribenzaldehyde and pyrrole in glacial acetic acid in the presence of FeCl3 leads to the formation of TPOP-1, which is a highly porous and robust material, and which exhibits a high surface area and bimodal pore sizes ranging from large micropores to mesopores. The presence of porphyrin and triazine functionality within the network structure enables formation of electron-donating basic N-sites at the surface of the porous organic framework and thus favors the adsorption of Lewis acidic CO2 molecules and decoration of the material by palladium nanoparticles at its surface to form Pd-TPOP-1. TPOP-1 showed good CO2 storage capacity (6.2 mmol g−1 or 27.3 wt% at 3 bar/273 K), suggesting its potential application in environmental clean-up. Moreover, this post Pd-functionalized material forms fine colloidal suspensions in organic solvent and exhibits high catalytic activity for Sonogashira cross-coupling of aryl halides with aryl alkynes under mild reaction conditions.