39617-00-0

Upstream product

• 5372-81-6 dimethyl aminoterephthalate 
• 52251-19-1 2-(N,N-dimethylamino)terephthlate dimethyl ester 
• 1026076-51-6 1,4-dimethyl 2-(methylamino)benzene-1,4-dicarboxylate 
• 10312-55-7 3-aminoterephthalic acid 
• 77-78-1 dimethyl sulfate 

Downstream Products

• 52251-19-1 2-(N,N-dimethylamino)terephthlate dimethyl ester 

Relevant academic research and scientific papers

Engineering Second Sphere Interactions in a Host-Guest Multicomponent Catalyst System for the Hydrogenation of Carbon Dioxide to Methanol

Many enzymes utilize interactions extending beyond the primary coordination sphere to enhance catalyst activity and/or selectivity. Such interactions could improve the efficacy of synthetic catalyst systems, but the supramolecular assemblies employed by biology to incorporate second sphere interactions are challenging to replicate in synthetic catalysts. Herein, a strategy is reported for efficiently manipulating outer-sphere influence on catalyst reactivity by modulating host-guest interactions between a noncovalently encapsulated transition-metal-based catalyst guest and a metal-organic framework (MOF) host. This composite consists of a ruthenium PNP pincer complex encapsulated in the MOF UiO-66 that is used in tandem with the zirconium oxide nodes of UiO-66 and a ruthenium PNN pincer complex to hydrogenate carbon dioxide to methanol. Due to the method used to incorporate the complexes in UiO-66, structure-activity relationships could be efficiently determined using a variety of functionalized UiO-66-X hosts. These investigations uncovered the beneficial effects of the ammonium functional group (i.e., UiO-66-NH3+). Mechanistic experiments revealed that the ammonium functionality improved efficiency in the hydrogenation of carbon dioxide to formic acid, the first step in the cascade. Isotope effects and structure-activity relationships suggested that the primary role of the ammonium functionality is to serve as a general Br?nsted acid. Importantly, the cooperative influence from the host was effective only with the functional group in close proximity to the encapsulated catalyst. Reactions carried out in the presence of molecular sieves to remove water highlighted the beneficial effects of the ammonium functional group in UiO-66-NH3+ and resulted in a 4-fold increase in activity. As a result of the modular nature of the catalyst system, the highest reported turnover number (TON) (19 ?000) and turnover frequency (TOF) (9100 h-1) for the hydrogenation of carbon dioxide to methanol are obtained. Moreover, the reaction was readily recyclable, leading to a cumulative TON of 100 ?000 after 10 reaction cycles.

PHOTO-REDOX TITANIUM CONTAINING ORGANIC FRAMEWORKS AND METHODS OF MAKING AND USE THEREOF

Disclosed herein are metal-organic frameworks and methods of making and use thereof.

Systematic variation of the optical bandgap in titanium based isoreticular metal-organic frameworks for photocatalytic reduction of CO2 under blue light

A series of metal-organic frameworks isoreticular to MIL-125-NH2 were prepared, where the 2-amino-terephthalate organic links feature N-alkyl groups of increasing chain length (from methyl to heptyl) and varying connectivity (primary and secondary). The prepared materials display reduced optical bandgaps correlated with the inductive donor ability of the alkyl substituent as well as high photocatalytic activity towards the reduction of carbon dioxide under blue illumination operating over 120 h. Secondary N-alkyl substitution (isopropyl, cyclopentyl and cyclohexyl) exhibits larger apparent quantum yields than the primary N-alkyl analogs directly related to their longer lived excited-state lifetime. In particular, MIL-125-NHCyp (Cyp = cyclopentyl) exhibits a small bandgap (Eg = 2.30 eV), a long-lived excited-state (τ = 68.8 ns) and a larger apparent quantum yield (Φapp = 1.80%) compared to the parent MIL-125-NH2 (Eg = 2.56 eV, Φapp = 0.31%, τ = 12.8 ns), making it a promising candidate for the next generation of photocatalysts for solar fuel production based on earth-abundant elements.

Synthesis of secondary and tertiary amine-containing MOFs: C-N bond cleavage during MOF synthesis

Secondary and tertiary amine-containing metal-organic frameworks (MOFs) have been synthesized, and unprecedented C-N bond cleavage phenomena were observed during MOF formation. Utilizing the secondary amine-containing ligand (BDC-NHMe), three new MOFs hav