A Method for Determining Incorporation Depth in Core-Shell UiO-66 Nanoparticles Synthesized Via Postsynthetic Exchange.

Postsynthetic exchange (PSE) is a key technique for integrating sensitive linkers into metal-organic frameworks (MOFs). Despite its importance, investigations into linker distributions have primarily focused on micrometer-sized crystals due to the analytical limitations, leaving nanoparticles less explored, although they are commonly synthesized and used in applications. In particular, the emergence of core-shell nanostructures via PSE has shown potential for applications in CO adsorption and selective catalysis.

Transition metal and lanthanide modified MOF-808 for barcode design.

This study explores the utilization of metal-organic frameworks (MOFs), particularly those incorporating lanthanide-based elements for their fluorescence capabilities, to create an advanced barcode system. By exploiting the modular nature of MOFs, we have developed a material capable of dynamic information encoding and robust against counterfeiting efforts. We introduce a novel barcode prototype that exhibits visible color shifts and fluorescence modulation when exposed to a specific sequence of chemical and thermal stimuli.

Highly Transparent, Yet Photoluminescent: 2D CdSe/CdS Nanoplatelet-Zeolitic Imidazolate Framework Composites Sensitive to Gas Adsorption.

In this work, thin composite films of zeolitic imidazolate frameworks (ZIFs) and colloidal two-dimensional (2D) core-crown CdSe/CdS nanoplatelet (NPL) emitters with minimal scattering are formed by a cycled growth method and yield highly transparent coatings with strong and narrow photoluminescence of the NPLs at 546 nm (FWHM: 25 nm) in a solid-state composite structure. The porous ZIF matrix acts as functional encapsulation for the emitters and enables the adsorption of the guest molecules water and ethanol. The adsorption and desorption of the guest molecules is then characterized by a reversable photoluminescence change of the embedded NPLs.

Correction: Tuning the optical properties of the metal-organic framework UiO-66 ligand functionalization.

Correction for 'Tuning the optical properties of the metal-organic framework UiO-66 ligand functionalization' by Marvin Treger , , 2023, , 6333-6341, https://doi.org/10.1039/D2CP03746G.

Transmission Porosimetry Study on High-quality Zr-fum-MOF Thin Films.

Crystalline Zr-fum-MOF (MOF-801) thin films of high quality are prepared on glass and silicon substrates by direct growth under solvothermal conditions. The synthesis is described in detail and the influence of different synthesis parameters such as temperature, precursor concentration, and the substrate type on the quality of the coatings is illustrated. Zr-fum-MOF thin films are characterized in terms of crystallinity, porosity, and homogeneity.

Synthesis and photochemical modification of monolayer thin MOF flakes for incorporation in defect free polymer composites.

Metal-organic frameworks (MOFs) with benzophenone linker molecules are characterized by their ability to undergo photochemical postsynthetic modification. While this approach opens up almost unlimited possibilities for tailoring materials to specific applications, the processability of the large particles is still lacking. In this work, we present a new approach to fabricate micro flakes of the stable Zr-bzpdc-MOF (bzpdc = benzophenone-4-4'-dicarboxylate) with a thickness of only a few monolayers.

Postsynthetic Photochemical Modification and 2D Structuring of Zr-MOF Thin Films Containing Benzophenone Linker Molecules.

For the fabrication of next-generation MOF-based devices the availability of highly adaptable materials in suitable shapes is crucial. Here, we present thin films of a metal-organic framework (MOF) containing photoreactive benzophenone units. Crystalline, oriented and porous films of the zirconium-based bzpdc-MOF (bzpdc=benzophenone-4-4'-dicarboxylate) are prepared by direct growth on silicon or glass substrates.

The influence of sample mass (scaling effect) on the synthesis and structure of non-graphitizing carbon (biochar) during the analytical pyrolysis of biomass.

The porous non-graphitizing carbon (NGC) known as biochar is derived from the pyrolytic conversion of organic precursors and is widely investigated due to its multifunctional applications. At present, biochar is predominantly synthesized in custom lab-scale reactors (LSRs) to determine the properties of carbon, while a thermogravimetric reactor (TG) is utilized for pyrolysis characterization. This results in inconsistencies in the correlation between the structure of biochar carbon and the pyrolysis process.

Cu-MOF-808 as a Sensing Material for Gaseous Hydrogen Sulfide.

The selective detection of hydrogen sulfide (H S) is an important task because of its potentially hazardous effects not only on the environment but also on human health. Here, we present the zirconium-based MOF-808, which was modified with copper salts, as a colorimetric sensor material for the visible, reversible and sensitive H S detection at room temperature. The copper cations, which are incorporated in the oxidation state +II, are installed at the inorganic building units (IBUs) of the framework so that they are accessible for interactions with H S.

Tuning the optical properties of the metal-organic framework UiO-66 ligand functionalization.

Metal-organic frameworks (MOFs) are a promising class of materials for optical applications, especially due to their modular design which allows fine-tuning of the relevant properties. The present theoretical study examines the Zr-based UiO-66-MOF and derivatives of it with respect to their optical properties. Starting from the well-known monofunctional amino- and nitro-functionalized UiO-66 derivatives, we introduce novel UiO-66-type MOFs containing bifunctional push-pull 1,4-benzenedicarboxylate () linkers.

Solvent-assisted linker exchange as a tool for the design of mixed-linker MIL-140D structured MOFs for highly selective detection of gaseous HS.

A MIL-140D- framework has been used as a highly stable backbone for the introduction of 4,4'-azobenzene dicarboxylic acid (H ) solvent-assisted ligand exchange (SALE). The implemented azo groups can serve as coordination sites for copper ions. These can exchange ligands with different gases, but show a high selectivity against HS, which makes this material promising for potential sensor applications.

Inside/Outside: Post-Synthetic Modification of the Zr-Benzophenonedicarboxylate Metal-Organic Framework.

The Zr-based metal-organic framework, Zr-bzpdc-MOF, contains the photoreactive linker molecule benzophenone-4,4'-dicarboxylate (bzpdc) which imparts the possibility for photochemical post-synthetic modification. Upon irradiation with UV light, the keto group of the benzophenone moiety will react with nearly every C-H bond-containing molecule. Within this paper, we further explore the photochemical reactivity of the Zr-bzpdc-MOF, especially with regard to which restrictions govern internal versus external reactions.

A Low-Temperature Approach for the Phase-Pure Synthesis of MIL-140 Structured Metal-Organic Frameworks.

In a systematic investigation, the synthesis of metal-organic frameworks (MOFs) with MIL-140 structure was studied. The precursors of this family of MOFs are the same as for the formation of the well-known UiO-type MOFs although the synthesis temperature for MIL-140 is significantly higher. This study is focused on the formation of Zr-based MIL-140 MOFs with terephthalic acid (H bdc), biphenyl-4,4'-dicarboxylic acid (H bpdc), and 4,4'-stilbenedicarboxylic acid (H sdc) and the introduction of synthesis field diagrams to discover parameters for phase-pure products.

Direct grafting-from of PEDOT from a photoreactive Zr-based MOF - a novel route to electrically conductive composite materials.

The postsynthetic potential of the two-dimensional metal-organic framework Zr-bzpdc-MOF which is based on the photoreactive molecule benzophenone-4,4'-dicarboxylic acid (H2bzpdc) is used here to selectively functionalize the MOF surface. We report the direct radical-induced oxidative grafting-from polymerization of the precursor EDOT on Zr-bzpdc-MOF, leading to an electrically conductive composite material and opening the road to a variety of applications.

A Calixarene-Based Metal-Organic Framework for Highly Selective NO Detection.

A calixarene-based metal-organic framework (Zr-cal, [Zr O (OH) (FA) ] (cal) ], FA=formate, cal=1,3-alt-25,26,27,28-tetrakis[(carboxy)methoxy]calixarene) was synthesized and characterized by single-crystal X-ray diffraction. The three-dimensional framework is a 4,6-connected network of gar topology and exhibits two equal but nonintersecting three-dimensional pore systems. It has a specific BET surface area of 670 m  g , and the calixarene cavities are accessible through the pore systems.

Delamination and Photochemical Modification of a Novel Two-Dimensional Zr-Based Metal-Organic Frameworks.

In this contribution we present a novel two-dimensional Zr-based metal-organic framework (MOF) which offers the possibility for delamination and post-synthetic photochemical modification at the linker molecule derived from benzophenone-4,4'-dicarboxylic acid (H bzpdc). The new Zr-bzpdc-MOF crystallizes in the orthorhombic system as crystals with rhombic shape. The structure was determined from single-crystal diffraction data.

Postsynthetic Modification of Metal-Organic Frameworks through Nitrile Oxide-Alkyne Cycloaddition.

Postsynthetic modification of metal-organic frameworks is an important method to tailor their properties. We report on the nitrile oxide-alkyne cycloaddition (NOAC) as a modification tool, a reaction requiring neither strained alkynes nor a catalyst. This is demonstrated with the reaction of nitrile oxides with PEPEP-PIZOF-15 and -19 at room temperature.

Post-synthetic modification of Zr-metal-organic frameworks through cycloaddition reactions.

Cycloaddition reactions are highly attractive for post-synthetic modification of metal-organic frameworks (MOFs). We report herein on cycloaddition reactions with PIZOF(R(1),R(2))s, which are porous interpenetrated Zr-based MOFs with Zr(6)O(4)(OH)(4)(CO(2))(12) as the nodes and the dicarboxylates (-)O(2)C[PE-P(R(1),R(2))-EP]CO(2)(-) (P: phenylene, E: ethynylene; R(1), R(2): side chains at the central phenylene unit) as the linkers. 1,3-Dipolar cycloaddition between the pendant ethyne moieties of PIZOF(OMe,OCH(2)C≡CH) and 4-methylbenzyl azide resulted in 98% conversion of the ethyne groups.

Highly oriented surface-growth and covalent dye labeling of mesoporous metal-organic frameworks.

Mesoporous amino-functionalized metal-organic framework thin films with the UiO-68 topology were grown in a highly oriented fashion on two different self-assembled monolayers on gold. The oriented MOF films were covalently modified with the fluorescent dye Rhodamine B inside the pore system, as demonstrated with size-selective fluorescence quenching studies. Our study suggests that mesoporous metal-organic frameworks are promising hosts for the covalent attachment of numerous functional moieties in a molecularly designed crystalline environment.

Porous interpenetrated zirconium-organic frameworks (PIZOFs): a chemically versatile family of metal-organic frameworks.

We present the synthesis and characterization of porous interpenetrated zirconium-organic frameworks (PIZOFs), a new family of metal-organic frameworks obtained from ZrCl(4) and the rodlike dicarboxylic acids HO(2)C[PE-P(R(1),R(2))-EP]CO(2) H that consist of alternating phenylene (P) and ethynylene (E) units. The substituents R(1),R(2) were broadly varied (alkyl, O-alkyl, oligo(ethylene glycol)), including postsynthetically addressable substituents (amino, alkyne, furan). The PIZOF structure is highly tolerant towards the variation of R(1) and R(2).

Modulated synthesis of Zr-based metal-organic frameworks: from nano to single crystals.

We present an investigation on the influence of benzoic acid, acetic acid, and water on the syntheses of the Zr-based metal-organic frameworks Zr-bdc (UiO-66), Zr-bdc-NH(2) (UiO-66-NH(2)), Zr-bpdc (UiO-67), and Zr-tpdc-NH(2) (UiO-68-NH(2)) (H(2) bdc: terephthalic acid, H(2) bpdc: biphenyl-4,4'-dicarboxylic acid, H(2) tpdc: terphenyl-4,4''-dicarboxylic acid). By varying the amount of benzoic or acetic acid, the synthesis of Zr-bdc can be modulated. With increasing concentration of the modulator, the products change from intergrown to individual crystals, the size of which can be tuned.