Application of metal − organic frameworks

Abstract

The burgeoning field of metal − organic frameworks or porous coordination polymers has received increasing interest in recent years. In the last decade these microporous materials have found several applications including storage and separation of gases, sensors, catalysis and functional materials. In order to better design new metal − organic frameworks and porous coordination polymers with specific functionalities a fundamental issue is to achieve a basic understanding of the relationship between molecular parameters and structures, preferred adsorption sites and properties by using using modern theoretical methods. The focus of this mini-review is a description of the potential and emerging applications of metal − organic frameworks.

Expanding the Variety of Zirconium‐based Inorganic Building Units for Metal–Organic Frameworks

“…Abstract: Tw on ew zirconium-based metal-organic frameworks with the composition [Zr 6 O 4 (OH) 4 (OAc) 6 (BDC) 3 ] (CAU-26) and [Zr 5 O 4 (OH) 4 (OAc) 4 (BDC) 2 ]( CAU-27) are reported, which were synthesized from acetic acid, ar arely utilized but green and sustainable solvent (BDC 2À :1 ,4benzenedicarboxylate). Structure determination aided by automated electron diffraction tomography revealed that CAU-26 is composed of layers of well-known {Zr 6 O 8 }c lusters interconnected by terephthalate ions.I nc ontrast CAU-27 exhibits at hree-dimensional structure with as of ar unknown type of one-dimensional inorganic building unit (IBU), which can be rationalized as condensed polyhedron-sharing chains of {Zr 6 O 8 }c lusters.C AU-26 occurs as an intermediate of the CAU-27 synthesis and can be isolated easily,w hen reaction temperature and time are decreased.…”

“…Thes tability originates from the strong coordination bond between highly charged Zr 4+ ions (strong Lewis acids) and oxygen anions from the ligand molecules (strong Lewis bases) and is in agreement with the HSAB (hard and soft acids and bases) principle. [4] However,amajor drawback is given by the synthesis conditions of zirconium MOFs,since the majority of reaction routes utilize the highly carcinogenic solvent N,N-dimethylformamide (DMF), which tends to decompose under hydrolysis of the amide bond at elevated temperatures or in an catalytic environment (e.g., acids,b ases,m etal ions). [4] However,amajor drawback is given by the synthesis conditions of zirconium MOFs,since the majority of reaction routes utilize the highly carcinogenic solvent N,N-dimethylformamide (DMF), which tends to decompose under hydrolysis of the amide bond at elevated temperatures or in an catalytic environment (e.g., acids,b ases,m etal ions).…”

“…Ther esults from TG ( Figures S25-S32) and variable temperature diffraction experiments (Figures S34-S41) prove the high thermal stability of the new MOFs ( % 400-470 8 8C) considering the phase transition upon acetate/ formate removal as non-destructive.F urthermore 24 hour stability tests within various different solvents and aqueous solutions across alarge pH range (1)(2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12) also showed that all materials exhibit outstanding chemical stability,e specially towards acids (stable in ap Hr ange of at least 1-11) and common organic liquids (Table S14). Ther esults from TG ( Figures S25-S32) and variable temperature diffraction experiments (Figures S34-S41) prove the high thermal stability of the new MOFs ( % 400-470 8 8C) considering the phase transition upon acetate/ formate removal as non-destructive.F urthermore 24 hour stability tests within various different solvents and aqueous solutions across alarge pH range (1)(2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12) also showed that all materials exhibit outstanding chemical stability,e specially towards acids (stable in ap Hr ange of at least 1-11) and common organic liquids (Table S14).…”

To Loop or Not to Loop: Influence of Hinge Flexibility on Self‐Assembly Outcomes for Acridine‐Based Triazolylpyridine Chelates with Zinc(II), Iron(II), and Copper(II)

“…Among the weak interactions employed to direct self‐assembly in artificial systems,, coordination bonds have played a pivotal role, producing many of the most complex– and promising materials, with applications in diverse areas such as biological targeting, chemical reactivity,– and gas management –. The booming field of metal–organic frameworks certainly attests to its importance –. Although the metal ions play a central role in defining the self‐assembly outcome both in terms of geometry and robustness, the ligands responsible for holding the metal ions apart at well‐defined distances are also critical in tuning the resulting self‐assembled architecture.…”

Synthesis, Crystal Structure and Luminescent Properties of 2D Zinc Coordination Polymers Based on Bis(1,2,4-triazol-1-yl)methane and 1,3-Bis(1,2,4-triazol-1-yl)propane

“…Coordination polymers and metal-organic frameworks attract the unceasing attention of researchers due to their wide range of potential applications [1][2][3][4][5][6]. One of the universal approaches to the construction of metal-organic frameworks uses a combination of metal ions with aromatic dior polycarboxylate donors and rigid or flexible N-donor bitopic ligands [7,8].…”