1312703-30-2

Upstream product

• 3638-73-1 2,5-dibromoaniline 
• 99768-12-4 4-methoxycarbonylphenylboronic acid 

Downstream Products

• 1312703-28-8 2’-amino-1,1’:4,1’’-terphenyl-4,4’’-dicarboxylic acid 

Relevant academic research and scientific papers

A drug-loaded nanoscale metal-organic framework with a tumor targeting agent for highly effective hepatoma therapy

Drug delivery systems with targeting agents for precise drug release in cancer therapy are very significant and important. Herein, we report the rational design and synthesis of a DOX (doxorubicin) loaded UiO-68-type of nanoscale metal-organic framework (NMOF) with a tumor targeting agent (folic acid, FA), DOX@UiO-68-FA (3), as a multifunctional drug delivery system for hepatoma (Hep G2) therapy via tail-vein injection. Compared to free DOX, FA-unloaded DOX@Mi-UiO-68 (2), 3 exhibits a much higher antitumor efficacy, which was confirmed by cell imaging, standard 3-(4,5-dimethylthiahiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) proliferation and in vivo experiments.

An Azobenzene-Modified Photoresponsive Thorium-Organic Framework: Monitoring and Quantitative Analysis of Reversible trans-cis Photoisomerization

Monitoring and quantification of the photoresponsive behavior of metal-organic frameworks that respond to a light stimulus are crucial to establish a clear structure-activity relationship related to light regulation. Herein, we report the first azobenzene-modified photoresponsive thorium-organic framework (Th-Azo-MOF) with the formula [Th6O4(OH)4(H2O)6L6] (H2L = (E)-2′-p-tolyldiazenyl-1,1′:4′,4′-terphenyl-4,4″-dicarboxylic acid), in which the utilization of a thorium cluster as a metal node leads to one of the largest pore sizes among all the azobenzene-containing metal-organic frameworks (MOFs). The phototriggered transformation of the trans isomer to the cis isomer is monitored and characterized quantitatively by comprehensive analyses of NMR and UV spectroscopy, which reveals that the maximum isomerization ratio of cisTh-Azo-MOF in the solid state is 19.7% after irradiation for 120 min, and this isomerization is reversible and can be repeated several times without apparent performance changes. Moreover, the isomerization-related difference in the adsorption of the Rhodamine B guest is also illustrated and a possible photoregulated mechanism is proposed. This work will shed light on new explorations for constructing functionalized actinide porous materials by the elegant combination of actinide nodes with tailored organic ligands and furthermore will provide a comprehensive understanding of photoisomerization processes in MOF solids and insight into the mechanism on photoregulated cargo adsorption and release by photoactive MOFs.

Crystalline Nanochannels with Pendant Azobenzene Groups: Steric or Polar Effects on Gas Adsorption and Diffusion?

An azobenzene-containing, zirconium-based metal-organic framework (AzoMOF), upon irradiation with ultraviolet (UV) light at 365 ± 10 nm, underwent trans-to-cis isomerization of its azobenzene pendants to furnish the cis-isomer content of 21% (AzoMOF21%) in 30 min at the photostationary state and underwent backward isomerization into AzoMOF1% upon either irradiation with visible light (420-480 nm) or heating. When the cis-isomer content increased, the diffusion rate and amount of CO2 adsorbed into the nanochannels of AzoMOF decreased considerably. When erythrosine B, a polarity-probing guest, was used, it showed a red shift upon exposure of AzoMOF20%?EB to visible light, indicating that the interior environment of AzoMOF turns less polar as the trans-isomer content becomes higher. In sharp contrast, the adsorption profiles of AzoMOF15% and AzoMOF1% for Ar having an analogous kinetic diameter to CO2 but no quadrupole moment and a smaller polarizability were virtually identical to one another. Therefore, it is likely that CO2 experiences a dominant effect of a polar effect rather than a steric effect in the crystalline nanochannels.

Zirconium-based MOF catalyst with double active sites and preparation method and application thereof

The invention discloses a zirconium-based MOF catalyst loaded with double active sites as well as a preparation method and an application of the zirconium-based MOF catalyst. The method comprises thefollowing steps: adding zirconium salt and an organic ligand into an organic solvent, taking organic acid as a regulator, and carrying out self-assembly reaction to obtain a metal organic framework; adding salicylaldehyde for aldehyde amine condensation to obtain chelating coordination sites, adding palladium salt, and performing coordination through an impregnation method; reducing the obtained MOF in hydrogen to obtain an MOF loaded with Pd nanoparticles; reacting MOF and zinc salt in an organic solvent, and obtaining the catalyst. The Pd-Zn-coated UiO-68-NH2-CH3 catalyst synthesized by thepreparation method disclosed by the invention has efficient catalytic activity in a tandem alcohol oxidation/aldehyde cyanosilylation reaction. According to the catalyst, a metal organic framework UiO-68-NH2-CH3 is constructed, Pd nanoparticles and Zn are loaded by taking the metal organic framework UiO-68-NH2-CH3 as a carrier, the loading capacity of the Pd nanoparticles is 4-8wt%, and the loading capacity of the Zn is 3-5wt%.

Amino Acid-Functionalized Metal-Organic Frameworks for Asymmetric Base–Metal Catalysis

We report a strategy to develop heterogeneous single-site enantioselective catalysts based on naturally occurring amino acids and earth-abundant metals for eco-friendly asymmetric catalysis. The grafting of amino acids within the pores of a metal-organic framework (MOF), followed by post-synthetic metalation with iron precursor, affords highly active and enantioselective (>99 % ee for 10 examples) catalysts for hydrosilylation and hydroboration of carbonyl compounds. Impressively, the MOF-Fe catalyst displayed high turnover numbers of up to 10 000 and was recycled and reused more than 15 times without diminishing the enantioselectivity. MOF-Fe displayed much higher activity and enantioselectivity than its homogeneous control catalyst, likely due to the formation of robust single-site catalyst in the MOF through site-isolation.

Single-Site Cobalt-Catalyst Ligated with Pyridylimine-Functionalized Metal-Organic Frameworks for Arene and Benzylic Borylation

We report a highly active single-site heterogeneous cobalt-catalyst based on a porous and robust pyridylimine-functionalized metal-organic frameworks (pyrim-MOF) for chemoselective borylation of arene and benzylic C-H bonds. The pyrim-MOF having UiO-68 topology, constructed from zirconium-cluster secondary building units and pyridylimine-functionalized dicarboxylate bridging linkers, was metalated with CoCl2 followed by treatment of NaEt3BH to give the cobalt-functionalized MOF-catalyst (pyrim-MOF-Co). Pyrim-MOF-Co has a broad substrate scope, allowing the C-H borylation of halogen-, alkoxy-, alkyl-substituted arenes as well as heterocyclic ring systems using B2pin2 or HBpin (pin = pinacolate) as the borylating agent to afford the corresponding arene- or alkyl-boronate esters in good yields. Pyrim-MOF-Co gave a turnover number (TON) of up to 2500 and could be recycled and reused at least 9 times. Pyrim-MOF-Co was also significantly more robust and active than its homogeneous control, highlighting the beneficial effect of active-site isolation within the MOF framework that prevents intermolecular decomposition. The experimental and computational studies suggested (pyrim?-)CoI(THF) as the active catalytic species within the MOF, which undergoes a mechanistic pathway of oxidative addition, turnover limiting σ-bond metathesis, followed by reductive elimination to afford the boronate ester.

Metal-organic frameworks containing nitrogen-donor ligands for efficient catalytic organic transformations

Metal-organic framework (MOFs) compositions based on nitrogen donor-based organic bridging ligands, including ligands based on 1,3-diketimine (NacNac), bipyridines and salicylaldimine, were synthesized and then post-synthetically metalated with metal precursors, such as complexes of first row transition metals. Metal complexes of the organic bridging ligands could also be directly incorporated into the MOFs. The MOFs provide a versatile family of recyclable and reusable single-site solid catalysts for catalyzing a variety of asymmetric organic transformations. The solid catalysts can also be integrated into a flow reactor or a supercritical fluid reactor.

Catalysis through Dynamic Spacer Installation of Multivariate Functionalities in Metal-Organic Frameworks

We demonstrate herein a facile strategy to engineer versatile catalytically active coordination interspace in the same primitive metal-organic framework (MOF) for variable heterogeneous catalysis. Different functional ligands can be reversibly inserted into and removed from proto-LIFM-28 individually or successively to bring in single or binary catalytic sites for specific reactions and switch the parent MOF to multipurpose catalysts. Alcohol-oxidation, Knoevenagel-condensation, click, acetal, and Baylis-Hillman reactions are achievable through simple exchange of a single catalytic spacer, while sequential or stepwise reactions are designable via selective combination of two catalytic spacers with different functionalities, thus making proto-LIFM-28 a multivariate MOF for multiuse and economic catalysis.

Different functional group modified zirconium frameworks for the photocatalytic reduction of carbon dioxide

Conversion of carbon dioxide (CO2) into useful chemicals is an important and urgent task from the energy and environment perspective. Herein, through a post-synthetic modification (PSM) approach, we synthesized three new metal-organic frameworks (MOFs) UiO-68-PSMs with different functional groups, namely, UiO-68-F, UiO-68-CH3 and UiO-68-OCH3, for the photocatalytic reduction of CO2. By introducing electron-withdrawing and electron-donating groups, UiO-68-PSMs showed different performance for the selective photocatalytic reduction of CO2 to CO because of change in charge separation and band gap of UiO caused by the presence of different functional groups.

Thermally activated delayed fluorescence of a Zr-based metal-organic framework

The first metal-organic framework exhibiting thermally activated delayed fluorescence (TADF) was developed. The zirconium-based framework (UiO-68-dpa) uses a newly designed linker composed of a terphenyl backbone, an electron-accepting carboxyl group, and an electron-donating diphenylamine and exhibits green TADF emission with a photoluminescence quantum yield of 30% and high thermal stability.