Probing Defects in Covalent Organic Frameworks.

Defects in covalent organic frameworks (COFs) play a pivotal role in determining their properties and performance, significantly influencing interactions with adsorbates, guest molecules, and substrates as well as affecting charge carrier dynamics and light absorption characteristics. The present review focuses on the diverse array of techniques employed for characterizing and quantifying defects in COFs, addressing a critical need in the field of materials science. As will be discussed in this review, there are basically two types of defects referring either to missing organic moieties leaving free binding groups in the material or structural imperfections resulting in lower crystallinity, grain boundary defects, and incomplete stacking.

Correction: Defect-enabling zirconium-based metal-organic frameworks for energy and environmental remediation applications.

Correction for 'Defect-enabling zirconium-based metal-organic frameworks for energy and environmental remediation applications' by Saba Daliran , , 2024, https://doi.org/10.1039/d3cs01057k.

Defect-enabling zirconium-based metal-organic frameworks for energy and environmental remediation applications.

This comprehensive review explores the diverse applications of defective zirconium-based metal-organic frameworks (Zr-MOFs) in energy and environmental remediation. Zr-MOFs have gained significant attention due to their unique properties, and deliberate introduction of defects further enhances their functionality. The review encompasses several areas where defective Zr-MOFs exhibit promise, including environmental remediation, detoxification of chemical warfare agents, photocatalytic energy conversions, and electrochemical applications.

A Porphyrin-Based Covalent Organic Framework as Metal-Free Visible-LED-Light Photocatalyst for One-Pot Tandem Benzyl Alcohol Oxidation/Knoevenagel Condensation.

A porphyrin-based covalent organic framework (COF), namely Porph-UOZ-COF (UOZ stands for the University of Zabol), has been designed and prepared via the condensation reaction of 5,10,15,20-tetrakis-(3,4-dihydroxyphenyl)porphyrin (DHPP) with 1,4-benzenediboronic acid (DBBA), under the solvothermal condition. The solid was characterized by spectroscopic, microscopic, and powder X-ray diffraction techniques. The resultant multifunctional COF revealed an outstanding performance in catalyzing a one-pot tandem selective benzylic C-H photooxygenation/Knoevenagel condensation reaction in the absence of additives or metals under visible-LED-light irradiation.

Evaluation of cytotoxicity, loading, and release activity of paclitaxel loaded-porphyrin based metal-organic framework (PCN-600).

Considering the inducement side impacts and precipitation of continual doses in conventional therapeutic treatments, there is an urgent need in the field of drug delivery for novel designs of biocompatible carriers with wide loading dimensions and particularly the ability to control their drug release. In this work, we succeeded in synthesizing an iron-based organic metal framework based on iron-porphyrin (PCN-600) through a solvothermal method to function as a drug delivery system (DDS). According to SEM results, PCN-600 crystals a hexagonal-rod shaped morphology with the length of 300 nm and width of 100-300 nm.

Recent Advances in the Use of Covalent Organic Frameworks as Heterogenous Photocatalysts in Organic Synthesis.

Organic photochemistry is intensely developed in the 1980s, in which the nature of excited electronic states and the energy and electron transfer processes are thoroughly studied and finally well-understood. This knowledge from molecular organic photochemistry can be transferred to the design of covalent organic frameworks (COFs) as active visible-light photocatalysts. COFs constitute a new class of crystalline porous materials with substantial application potentials.

Correction: Metal-organic framework (MOF)-, covalent-organic framework (COF)-, and porous-organic polymers (POP)-catalyzed selective C-H bond activation and functionalization reactions.

Correction for 'Metal-organic framework (MOF)-, covalent-organic framework (COF)-, and porous-organic polymers (POP)-catalyzed selective C-H bond activation and functionalization reactions' by Saba Daliran , , 2022, https://doi.org/10.1039/d1cs00976a.

CsCuI Nanoparticles Incorporated within a Mesoporous Metal-Organic Porphyrin Framework as a Catalyst for One-Pot Click Cycloaddition and Oxidation/Knoevenagel Tandem Reaction.

Metal-organic frameworks (MOFs) and metal halide perovskites are currently under much investigation due to their unique properties and applications. Herein, an innovative strategy has been developed combining an iron-porphyrin MOF, PCN-222(Fe), and an -grown CsCuI nontoxic lead-free halide perovskite based on an earth-abundant metal that becomes incorporated within the MOF channels [CsCuI@PCN-222(Fe)]. Encapsulation was designed to decrease and control the particle size and increase the stability of CsCuI.

Metal-organic framework (MOF)-, covalent-organic framework (COF)-, and porous-organic polymers (POP)-catalyzed selective C-H bond activation and functionalization reactions.

Although C-H functionalization is one of the simplest reactions, it requires the use of highly active and selective catalysts. Recently, C-H-active transformations using porous materials such as crystalline metal-organic frameworks (MOFs) and covalent-organic frameworks (COFs) as well as amorphous porous-organic polymers (POPs) as new emerging heterogeneous catalysts have attracted significant attention due to their promising activity and potential material tunability. These porous solids offer exceptional structural uniformity, facile tunability and permanent porosity.

A Pyridyltriazol Functionalized Zirconium Metal-Organic Framework for Selective and Highly Efficient Adsorption of Palladium.

This work reports the synthesis of pyridyltriazol-functionalized UiO-66 (UiO stands for University of Oslo), namely, UiO-66-Pyta, from UiO-66-NH through three postsynthetic modification (PSM) steps. The good performance of the material derives from the observation that partial formylation (∼21% of -NHCHO groups) of HBDC-NH by DMF, as persistent impurity, takes place during the synthesis of the UiO-66-NH. Thus, to enhance material performance, first, the as-synthesized UiO-66-NH was deformylated to give pure UiO-66-NH.

Brønsted-Lewis dual acid sites in a chromium-based metal-organic framework for cooperative catalysis: Highly efficient synthesis of quinazolin-(4H)-1-one derivatives.

A novel MIL-101(Cr) (MIL, Matérial Institut Lavoisier) supported propyl carboxylic acid, denoted here as MIL-101(Cr)-NH-CO-Pr-COOH, has been fabricated by post-synthetic modifications of nitro-functionalized MIL-101(Cr), MIL-101(Cr)-NO. The resulting MOF was successfully characterized by using FT-IR, XRD, N adsorption-desorption, H NMR, SEM, ICP-OES, elemental analysis and TGA. Then, the prepared solid was used as an extremely highly effective multifunctional catalyst for the one-pot three-component synthesis of quinazolin-4(1H)-one derivatives as biologically active nitrogen heterocyclic compounds under solvent-free conditions.

New porphyrins: synthesis, characterization, and computational studies.

New trans-AB-porphyrins substituted at phenyl positions were synthesized from 4-methylphthalic acid as a starting material through sequential multistep reactions. These macrocycles were characterized by H NMR, C NMR, F NMR, H-H COSY NMR, and MALDI-TOF mass spectrometry. Computational studies were performed on the porphyrins to investigate various factors such as structural features, electronic energy, energy gaps, and aromaticity.

A hybrid material composed of an amino-functionalized zirconium-based metal-organic framework and a urea-based porous organic polymer as an efficient sorbent for extraction of uranium(VI).

An amino-functionalized zirconium metal-organic framework was composed with a 3D urea-based porous organic polymer to give a hybrid material termed UiO-66-NH/urea-POP. The material was characterized by Fourier transform infrared spectroscopy, powder X-ray diffraction, scanning electron microscopy, and Brunauer-Emmett-Teller surface area measurements. It is shown to be a viable sorbent for solid-phase extraction of uranium from water samples.

Cu(II)-Schiff base covalently anchored to MIL-125(Ti)-NH as heterogeneous catalyst for oxidation reactions.

MIL-125(Ti)-NH has been modified by reaction of salicylaldehyde with the terephthalate amino groups to form a salicylideneimine that act as ligand of Cu. The success of the postsynthetic modification was assessed by FTIR spectroscopy of the MIL-125(Ti)-NH-Sal-Cu and by analysis by H NMR spectroscopy of the organic linkers upon dissolution of MIL-125(Ti)-NH-Sal-Cu. In comparison with parent MIL-125(Ti)-NH and MIL-125(Ti)-NH-Sal, that exhibit a poor activity, the presence of the Cu-Schiff base complex in MIL-125(Ti)-NH-Sal-Cu catalyst for the oxidation of 1-phenylethanol by tert-butylhydroperoxyde (TBHP, 3 eq.