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 CO2 adsorption and selective catalysis. This study addresses this gap by investigating the formation of core-shell structures on nanoparticles under diffusion-controlled PSE conditions. By analyzing volume-to-surface ratios and conducting time-dependent experiments, we confirmed that these conditions facilitate the development of core-shell architectures. We also developed a straightforward method to calculate the minimum incorporation depth using basic parameters such as particle size and the total amount of incorporated linker. The accuracy of our approach was validated against data obtained from transmission electron microscopy coupled with energy-dispersive X-ray spectroscopy. These findings enhance the understanding of PSE in MOF nanoparticles and open up promising avenues for developing advanced MOF core-shell structures for various applications.

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. The barcode is composed of MOF-808, which is modified with transition metals like iron or cobalt, and europium cations. These components are embedded within polyvinylidene fluoride (PVDF) to form a composite. This embedding process ensures that the MOF particles remain reactive to specific trigger molecules, enabling a distinct read-out sequence. The decoding process, involving exposure to ammonia, heating at 120 °C, and treatment with HCl, triggers observable changes in fluorescence and color, depending on the transition metal used. Our investigations with Eu,Co-MOF-808, and Eu,Fe-MOF-808 composites have resulted in the creation of a barcode prototype that demonstrates the feasibility of using europium-modified and unmodified transition metal modified MOF-808@PVDF composites for enhanced security applications.

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. The transmittance of the composite films exceeds the values of uncoated glass at visible wavelengths where the NPL emitters show no absorption (>540 nm) and renders them anti-reflective coatings. At NPL absorption wavelengths (440-540 nm), the transmittance of the thin composite film-coated glass lies close to the transmittance of uncoated glass. The fast formation of innovative, smooth NPL/ZIF composite films without pre-polymerizing the colloidal 2D nanostructures first provides a powerful tool toward application-oriented photoluminescence-based gas sensing.

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

Correction for 'Tuning the optical properties of the metal-organic framework UiO-66 via ligand functionalization' by Marvin Treger et al., Phys. Chem. Chem. Phys., 2023, 25, 6333-6341, https://doi.org/10.1039/D2CP03746G.

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. The crystalline and nanoporous flakes form dispersions in acetone that are stable for months. Embedding the flakes in polymer composites was investigated as one of many possible applications. Zr-bzpdc-MOF micro flakes were decorated with poly(dimethylsiloxane) (PDMS) via a photochemical postsynthetic modification and incorporated into silicon elastomers. The PDMS functionalization allows covalent cross-linking between the MOF and the polymer while maintaining the porosity of the MOF. The resulting hybrid materials provide defect-free interfaces and show preferential adsorption of CO2 over CH4, making them attractive for gas separation or sensing applications. The work should serve as a basis for bringing bzpdc-MOFs into real-world applications - in polymeric membranes, but also beyond.

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. Dense films of optical quality are obtained. The sorption behavior of the thin films is studied with various adsorptives. It can be easily monitored by measuring the transmission of the films in gas flows of different compositions. This simple transmission measurement at only one wavelength allows a very fast evaluation of the adsorption properties of thin films as compared to traditional sorption methods. The sorption behavior of the thin films is compared with the sorption properties of Zr-fum-MOF powder samples.

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. If a TG reactor can also be used as an LSR for biochar synthesis, then the process characteristics and the properties of the synthesized NGC can be simultaneously investigated. It also eliminates the need for expensive LSRs in the laboratory, improves the reproducibility, and correlatability of pyrolysis characteristics with the properties of the resulting biochar carbon. Furthermore, despite numerous TG studies on the kinetics and characterization of biomass pyrolysis, none have questioned how the properties of biochar carbon vary due to the influence of the starting sample mass (scaling) in the reactor. Herein, with a lignin-rich model substrate (walnut shells), TG is utilized as an LSR, for the first time, to investigate the scaling effect starting from the pure kinetic regime (KR). The changes in the pyrolysis characteristics and the structural properties of the resultant NGC with scaling are concurrently traced and comprehensively studied. It is conclusively proven that scaling influences the pyrolysis process and the NGC structure. There is a gradual shift in pyrolysis characteristics and NGC properties from the KR until an inflection mass of ∼200 mg is reached. After this, the carbon properties (aryl-C%, pore characteristics, defects in nanostructure, and biochar yield) are similar. At small scales (≲100 mg), and especially near the KR (≤10 mg) carbonization is higher despite the reduced char formation reaction. The pyrolysis is more endothermic near KR with increased emissions of CO2 and H2O. For a lignin-rich precursor, at masses above inflection point, TG can be employed for concurrent pyrolysis characterization and biochar synthesis for application-specific NGC investigations.

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. Via a subsequent photochemical modification of the Zr-bzpdc-MOF films, various properties can be tuned postsynthetically by covalent attachment of modifying agents. Apart from the modification with small molecules, also grafting-from polymerization reactions are possible. In a further extension, 2D structuring and photo-writing of defined structures is also possible, for example by using a photolithographic approach, paving the way towards micro-patterned MOF surfaces.

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

The selective detection of hydrogen sulfide (H2 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 H2 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 H2 S. The activated copper doped MOF-808 powder shows significant and fast color change in the presence of H2 S, which can be detected by UV-vis spectroscopy. Moreover, the detection process is reversible by heating the material to 120 °C under ambient conditions leading to its decolorization. The detection performance of the material was studied by in situ UV-vis measurements in a reaction chamber. The material was able to respond to 100 ppm H2 S in several cycles of exposure and heating to 120 °C under moist air conditions in a defined wavelength range. This reversibility is very uncommon for copper-based H2 S sensing reactions and highlights the potential of MOFs as selective sensing materials.

Tuning the optical properties of the metal-organic framework UiO-66 via 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 (bdc) linkers. The successful synthesis of such a novel UiO-66 derivative is also reported. It was carried out using a para-nitroaniline (PNA)-based bdc-analogue linker. Applying density functional theory (DFT), suitable models for all UiO-66-MOF analogues were generated by assessing different exchange-correlation functionals. Afterwards, HSE06 hybrid functional calculations were performed to obtain the electronic structures and optical properties. The detailed HSE06 electronic structure calculations were validated with UV-Vis measurements to ensure reliable results. Finally, the refractive index dispersion of the seven UiO-66-type materials is compared, showing the possibility to tailor the optical properties by the use of functionalized linker molecules. Specifically, the refractive index can be varied over a wide range from 1.37 to 1.78.

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. We show that apart from reactions with C-H bond-containing molecules, the MOF reacts also with water. By studying the reactivity versus linear alcohols we find a clear delineation in that shorter alcohol molecules (up to butanol as a borderline case) react with photoexcited keto groups throughout the whole crystals whereas longer ones react only with surface-standing keto groups. In addition, we show that with the alkanes n-butane to n-octane, the reaction is restricted to the outer surface. We hypothesize that the reactivity of the Zr-bzpdc-MOF versus different reagents depends on the accessibility of the pore system which in turn depends mainly on the size of the reagents and on their polarity. The possibility to direct the post-synthetic modification of the Zr-bzpdc-MOF (selective modification of the whole pore system versus surface modification) gives additional degrees of freedom in the design of this metal-organic framework for shaping and for applications.

Solvent-assisted linker exchange as a tool for the design of mixed-linker MIL-140D structured MOFs for highly selective detection of gaseous H2S.

A MIL-140D-sdc framework has been used as a highly stable backbone for the introduction of 4,4'-azobenzene dicarboxylic acid (H2 abdc) via 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 H2S, which makes this material promising for potential sensor applications.

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 (H2 bdc), biphenyl-4,4'-dicarboxylic acid (H2 bpdc), and 4,4'-stilbenedicarboxylic acid (H2 sdc) and the introduction of synthesis field diagrams to discover parameters for phase-pure products. In this context, a MIL-140 network with H2 sdc as linker molecule is first reported. Additionally, an important aspect is the reduction of the synthesis temperature to make MIL-140 MOFs more accessible even though linkers with a more delicate nature are used. The solvothermal syntheses were conducted in highly concentrated reaction mixtures whereby a targeted synthesis to yield the MIL-140 phase is possible. Furthermore, the effect of the often-used modulator approach is examined for these systems. Finally, the characteristics of the synthesized MOFs are compared with physisorption measurements, thermogravimetric analyses, and scanning electron microscopy.

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.

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 (H2 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. The MOF is stable up to 300 °C in air and exhibits a moderate BET surface area of 650 m2 g-1 . The material can be obtained as thin sheets of a few nanometer thickness. Single crystals were modified post-synthetically, exploiting the intrinsic reactivity of the benzophenone group with C-H bond containing molecules. In this way, the surface properties of the MOF crystals (e.g., dispersibility in different solvents) can be changed drastically. Delamination and adaptation of the surface chemistry open up novel ways for shaping MOFs, for example, for the incorporation into polymer composites, and pave the way for various applications.

A Calixarene-Based Metal-Organic Framework for Highly Selective NO2 Detection.

A calixarene-based metal-organic framework (Zr-cal, [Zr6 O4 (OH)4 (FA)6 ]2 (cal)3 ], 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 m2 g-1 , and the calixarene cavities are accessible through the pore systems. The exposed calixarenes can be used for the visual detection and encapsulation of NO2 through the formation of deeply colored charge-transfer complexes inside the MOF. The highly selective complexation was analyzed by UV/Vis and IR spectroscopy, and the stability of the material was confirmed by powder X-ray diffraction and 1 H NMR spectroscopy. Finally, the MOF was used as a sensor material in a home-made sensor cell and showed high sensitivity for NO2 .

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. PIZOF-15 and -19 are porous Zr-based MOFs (BET surface areas 1740 and 960 m2 g-1, respectively) consisting of two mutually interpenetrating UiO-type frameworks with linkers of the type -O2C[PE-P(R1,R2)-EP]CO2- (P, phenylene; E, ethynylene; R1 and R2, side chains at the central benzene ring with R1 = R2 = OCH2C≡CH or R1 = OCH2C≡CH and R2 = O(CH2CH2O)3Me). Their syntheses, using benzoic acid as a modulator, and their characterization are reported herein. The propargyloxy (OCH2C≡CH) side chains contain the ethyne moieties needed for NOAC. Formation of nitrile oxides through oxidation of oximes in aqueous ethanolic solution in the presence of PEPEP-PIZOF-15 and -19 resulted in the reaction of 96-100% of the ethyne moieties to give isoxazoles. Thereby the framework was preserved. The type of nitrile oxide RCNO was greatly varied with R being isopentyl, tolyl, 2-pyridyl, and pentafluorophenyl. A detailed NMR spectroscopic investigation showed the formation of the 3,5-disubstituted isoxazole to be clearly favored (≥96%) over that of the constitutional isomeric 3,4-disubstituted isoxazole, except for one example.

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. Reactions of PIZOF(OMe,O(CH(2))(3)furan) with maleimide, N-methylmaleimide, and N-phenylmaleimide converted 98, 99, and 89% of the furan moieties into the Diels-Alder adducts. However, no reaction occurred with maleic anhydride. High-resolution (1)H NMR spectra were crucial in determining the conversion and identifying the reaction products. Of all the reagents (NaOD/D(2)O, D(2)SO(4), Bu(4)NF, CsF, CsF/DCl, and KHF(2)) tested for the disassembly of the PIZOFs in [D(6)]DMSO, the combination of CsF and DCl was found to be the best. The disassembly at room temperature was fast (5-15 min), and after the addition of K(2)CO(3) the (1)H NMR data were identical to those of the diacids (=protonated linkers) dissolved in pure DMSO. This allowed for simple structure elucidation through data comparison. CsF/DCl dissolves not only PIZOFs but also the hydrolytically very stable UiO-66.

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). This together with the modular synthesis of the diacids offers a facile tuning of the chemical environment within the pores. The PIZOF structure was solved from single-crystal X-ray diffraction analysis. The PIZOFs are stable under ambient conditions. PIZOF-2, the PIZOF prepared from HO(2)C[PE-P(OMe,OMe)-EP]CO(2)H, served as a prototype to determine thermal stability and porosity. It is stable up to 325 °C in air as determined by using thermogravimetry and powder X-ray diffraction. Argon sorption isotherms on PIZOF-2 revealed a Brunauer-Emmett-Teller (BET) surface area of 1250 m(2) g(-1) and a total pore volume of 0.68 cm(3) g(-1).