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Surface Functionalization of Metal-Organic Frameworks for Improved Moisture Resistance
Published on: September 5, 2018
Formate-based magnetic metal-organic frameworks templated by protonated amines
Zheming Wang1, Keli Hu, Song Gao
1Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. China. zmw@pku.edu.cn
Advanced Materials (Deerfield Beach, Fla.)
|March 30, 2010
Summary
Researchers explored 3D metal formate frameworks templated by amines. They discovered these versatile materials exhibit tunable structures and diverse magnetic, dielectric, porous, and optical properties, highlighting formate
Area of Science:
- Materials Science
- Coordination Chemistry
- Supramolecular Chemistry
Background:
- 3D metal formate frameworks are an understudied class of molecule-based materials.
- The structure and properties of these frameworks are influenced by templating cations.
- Formate, a simple carboxylate, offers biocompatibility and environmental friendliness.
Purpose of the Study:
- To systematically investigate 3D divalent metal formate frameworks templated by protonated amines.
- To explore the structural diversity and resulting properties of these novel frameworks.
- To highlight the potential of formate-based materials in constructing functional molecule-based systems.
Main Methods:
- Synthesis of six distinct metal formate frameworks using protonated amine templates.
- Structural characterization of the resulting frameworks, including topological analysis.
- Evaluation of magnetic, dielectric, porous, and optical properties.
Main Results:
- Successfully synthesized six types of metal formate frameworks with diverse topologies (chiral, perovskite, bi-nodal, diamond).
- Demonstrated the malleability of metal formate frameworks, with structures dependent on templating cation characteristics.
- Observed promising and abundant magnetic, dielectric, porous, and optical properties, often in combination.
Conclusions:
- Protonated amine-templated metal formate frameworks offer significant structural diversity and tunable properties.
- Formate-based materials are highly promising for developing advanced molecule-based materials.
- These findings underscore the potential of formate as a versatile building block in materials chemistry.
Related Concept Videos
01:23Properties of Organometallic Compounds
Organometallic compounds are compounds that contain a carbon–metal bond. Carbon belongs to an organyl group like alkyl, aryl, allyl, or benzyl groups. The metal can be from Group I or Group II of the periodic table, a transition metal, or a semimetal.
01:25Basicity of Heterocyclic Aromatic Amines
Heterocyclic amines, where the N atom is a part of an alicyclic system, are similar in basicity to alkylamines. Interestingly, the heterocyclic amine having a nitrogen atom as part of an aromatic ring has much less basicity than its corresponding alicyclic counterpart. For this reason, as presented in Figure 1, piperidine (pKb = 2.8) is significantly more basic than pyridine (pKb = 8.8).
01:16Aldehydes and Ketones with Amines: Imine and Enamine Formation Overview
Primary amines react with carbonyl compounds—aldehydes and ketones—to generate imines. Imines consist of a C=N double bond and are named Schiff bases after its discoverer—the German chemist Hugo Schiff. On the other hand, secondary amines react with carbonyl compounds to give enamines. In enamines, the presence of a C=C double bond adjacent to the nitrogen atom leads to the delocalization of the lone pair.
01:23Aldehydes and Ketones with Amines: Imine Formation Mechanism
Imine formation involves the addition of carbonyl compounds to a primary amine. It begins with the generation of carbinolamine through a series of steps involving an initial nucleophilic attack and then several proton transfer reactions. The second part includes the elimination of water, as a leaving group, to give the imine.
Imines are formed under mildly acidic conditions. A pH of 4.5 is ideal for the reaction.
If the pH is low or the solution is too acidic, the reaction slows down in the...
Imines are formed under mildly acidic conditions. A pH of 4.5 is ideal for the reaction.
If the pH is low or the solution is too acidic, the reaction slows down in the...
01:19Structure of Amines
The hybridized nitrogen atom in amines possesses a lone pair of electrons and is bound to three substituents with a bond angle of around 108°, which is less than the tetrahedral angle of 109.5°. However, the C–N–H bond angle is slightly larger at 112°, with a carbon–nitrogen bond length of 147 pm. This carbon–nitrogen bond length of of amines is longer than the carbon–oxygen bond of alcohols (143 pm) but shorter than alkanes’ carbon–carbon bond (154 pm). These aspects are illustrated in Figure...
01:19Amines to Amides: Acylation of Amines
Various carboxylic acid derivatives (such as acid chlorides, esters, and anhydrides) can be used for the acylation of amines to yield amides. The reaction requires two equivalents of amines. The first amine molecule functions as a nucleophile and attacks the carbonyl carbon to produce a tetrahedral intermediate. This is followed by the loss of the leaving group and restoration of the C=O bond.
Next, the second equivalent of amine serves as a Brønsted base and deprotonates the quaternary amide...
Next, the second equivalent of amine serves as a Brønsted base and deprotonates the quaternary amide...