Exxonmobil Technology and Engineering Company

Exxonmobil Research and Engineering Company

Mary S Abdulkarim

Joseph M Falkowski

Simon Christopher Weston

Carter W Abney

Mobae Afeworki

Yogesh V Joshi

Randall J Meyer

Aaron Sattler

Michele L Paccagnini

Wesley Sattler

Matthew T Kapelewski

Gerardo J Majano Sanchez

Aaron W Peters

Anna C Ivashko

Julie J Seo

Metal-organic framework materials (MOFs) are highly porous entities comprising a multidentate organic ligand coordinated to multiple metal centers, typically as a coordination polymer. Crystallization may be problematic in some instances when secondary binding sites are present in the multidentate organic ligand. Multidentate organic ligands comprising first and second binding sites bridged together with a third binding site comprising a diimine moiety may alleviate these issues, particularly when using a preformed metal cluster as a metal source to form a MOF. Such MOFs may comprise a plurality of metal centers, and a multidentate organic ligand coordinated to the plurality of metal centers to define an at least partially crystalline network structure having a plurality of internal pores, and in which the multidentate organic ligand comprises first and second binding sites bridged together with a third binding site comprising a diimine moiety. Particular MOFs may comprise N,N'-di(1H-pyrazol-4-yl)ethane-1,2-diimine as a multidentate organic ligand.

Metal-organic framework materials comprising a diimine scaffold and methods for production thereof

Metal-organic framework materials (MOFs) are highly porous entities comprising a multidentate organic ligand coordinated to multiple metal centers, typically as a coordination polymer. Some highly porous MOFs lack stability at ambient conditions. MOFs having ambient condition stability may comprise a plurality of metal clusters (MO clusters, M=a metal), and a plurality of 4-(1H-pyrazol-4-yl)benzoate ligands coordinated to the plurality of metal clusters to define an at least partially crystalline network structure having a plurality of internal pores. Methods for synthesizing these MOFs may comprise combining a metal source, such as a preformed metal cluster, with 4-(1H-pyrazol-4-yl)benzoic acid, and reacting the preformed metal cluster with the 4-(1H-pyrazol-4-yl)benzoic acid to form a MOF having an at least partially crystalline network structure with a plurality of internal pores defined therein and comprising a plurality of metal clusters coordinated to a multidentate organic ligand comprising 4-(1H-pyrazol-4-yl)benzoate.

Metal-organic framework materials comprising a pyrazolylbenzoate ligand and methods for production thereof

Metal-organic framework materials (MOFs) are highly porous entities comprising a multidentate organic ligand coordinated to multiple metal centers, typically as a coordination polymer. MOFs may comprise a plurality of metal centers, and a multidentate organic ligand coordinated via at least two binding sites to the plurality of metal centers to define an at least partially crystalline network structure having a plurality of internal pores, and in which the multidentate organic ligand comprises first and second binding sites bridged together with a third binding site comprising a diimine moiety. The multidentate organic ligand may comprise a reaction product of a vicinal dicarbonyl compound and an amine-substituted salicylic acid to define the first, second and third binding sites. Particular MOFs may comprise 5,59'-(((1E,2E)-ethane-1,2-diylidene)bis-(azaneylylidene))bis(2-hydroxybenzoic acid) as a multidentate organic ligand.

Metal-organic framework materials comprising a diimine bis-salicylate scaffold and methods for production thereof

Metal-organic framework materials (MOFs) are highly porous entities comprising a multidentate organic ligand coordinated to multiple metal centers. MOFs having ambient condition stability may comprise a plurality of metal clusters comprising one or more MO clusters (M is a metal), and a plurality of 4-pyrazolecarboxylate ligands coordinated to the plurality of metal clusters to define an at least partially crystalline network structure having a plurality of internal pores. The MOFs may have a Pa3 symmetry, which upon activation may convert into Fm3m symmetry. Methods for synthesizing the MOFs may comprise combining a metal source, such as a preformed metal cluster, with 4-pyrazolecarboxylic acid, and reacting the preformed metal cluster with the 4-pyrazolecarboxylic acid to form a MOF having an at least partially crystalline network structure with a plurality of internal pores defined therein and comprising a plurality of metal clusters coordinated to a multidentate organic ligand comprising 4-pyrazolecarboxylate.

Metal-organic framework materials comprising a pyrazolylcarboxylate ligand and methods for production thereof

Provided herein are methods of novel methods of synthesizing a metal-organic framework system by vapor-phase appending of a plurality of ligands appended to a metal-organic framework. Also, provided are methods of recycling metal-organic framework systems by detaching the ligand and re-appending the same ligand or appending a different ligand to the metal-organic framework to provide a recycled or repurposed metal-organic framework system.

Methods of synthesizing and recycling metal-organic framework systems

A novel metal organic framework, EMM-39, is described having the structure of UiO-66 and comprising bisphosphonate linking ligands. EMM-39 has acid activity and is useful as a catalyst in olefin isomerization. Also disclosed is a process of making metal organic frameworks, such as EMM-39, by heterogeneous ligand exchange, in which linking ligands having a first bonding functionality in a host metal organic framework are exchanged with linking ligands having a second different bonding functionality in the framework.

Metal organic frameworks, their synthesis and use

A novel metal organic framework, EMM-42, is described having the structure of UiO-66 and comprising bisphosphonate linking ligands. EMM-42 has acid activity and is useful as a catalyst in olefin isomerization. Also disclosed is a process of making metal organic frameworks, such as EMM-42, by heterogeneous ligand exchange, in which linking ligands having a first bonding functionality in a host metal organic framework are exchanged with linking ligands having a second different bonding functionality in the framework.

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Palisades Park, NJ, United States of America

Mary S Abdulkarim