Molecular engineering for synthesizing novel structures of metal–organic frameworks with multifunctional properties

doi:10.1016/j.ccr.2009.07.020

Coordination Chemistry Reviews

Volume 253, Issues 23–24, December 2009, Pages 2891-2911

https://doi.org/10.1016/j.ccr.2009.07.020 Get rights and content

Abstract

Metal–organic frameworks (MOFs) which are constructed from metal ions or metal ion clusters and bridging organic linkers, have recently emerged as an important family of porous materials due to their unique structural and functional properties. This review provides the molecular engineering for synthesizing novel MOF structures and summarizes their potential applications. In this review, we present the promotion of the synthesis chemistry in this area and introduce the general methods and the important factor of organic template in the synthesis process. To obtain MOFs with high porosity, three strategies will be introduced. We also discuss how to functionalize the MOFs from two directions: chiral frameworks and frameworks constructed from rare earth metals. The burgeoning area of MOF membranes will also be introduced. Most applications of MOFs are based on their ability to function as hosts. The potential applications including hydrogen storage and methane storage, molecular separation, catalysis, and sensor, are summarized. It is expected that MOFs will provide extraordinary advantages over traditional porous materials and have an important and permanent impact on the future of porous compounds.

Introduction

During the past 10 years, metal–organic frameworks (MOFs, also known as porous coordination polymers (PCPs)) have attracted wide scientific attention, as can be seen from the increasing number of publications devoted to this field [1]. Such high interest is caused not only by the enormous variety of interesting molecular topologies but also owing to their excellent properties, with promising applications such as the storage of gases, molecular separation from the gaseous and liquid mixtures, catalysis, sometimes showing the enantioselectivity, and sensors for special classes of molecules [2], [3]. They also can be designed as multifunctional materials with excellent physical properties like magnetism, luminescence, and optoelectronics [4], [5], [6], [7], [8]. However, the majority of these applications are based on the ability of MOFs to behave as hosts for certain molecules. MOFs have already been tested as microporous materials with exceptionally high porosity, uniform but tunable pore size and with well-defined molecular adsorption sites. Many metal–organic frameworks are now reported in the literatures with surface areas greater than 1000 m² g⁻¹, while some surface areas reported in MOFs have exceeded 5000 m² g⁻¹, such as MIL-101, UMCM-1, etc. [9], [42]. One of the most important goals in the synthesis of new materials is to achieve real “design” and to obtain compounds with expected structures and properties.

Generally speaking, MOF structures have two main components: the organic linkers and the metal centers. The organic linkers considered as organic secondary building unit (SBU), act as “struts” that bridge metal centers considered as inorganic SBU, which in turn act as “joints” in the resulting MOF architecture [10], [11]. The two main components are connected to each other by coordination bonds, together with other intermolecular interactions, to form a network with a definite topology.

Metal centers in MOF structure are usually metal clusters, like metal–carboxylate clusters, metal–azolate clusters, etc. (Fig. 1) [12], [13], sometimes just metal atoms or rod-shaped clusters [11]. The coordination number and geometries of metal centers rule the inorganic SBU nodes in the target network. However, the challenge to produce the target network structure from the reactions of simple metal ion and organic linkers is that free metal ions contain too many binding sites and have little directional information. The promotion of inorganic synthesis chemistry to needed to solve this problem. The concept inorganic SBU borrowed from the description of zeolites facilitates the design and synthesis of the extended frameworks. The organic linkers are multidentate organic ligands, which are usually carboxylates, azoles, nitriles, etc. (Fig. 2) [10]. The ligands can also be designed for the nodes in the target network, and can be synthesized and modified by organic synthesis. The properties of the metal centers and linkers usually determine the function of the target material, like porosity, pore size, pore surface and other physical properties [2]. If the nodes of network are well-defined, the network structure could possibly be predicted (Fig. 3) [10], [14], [15]. However, there are a large number of possible structures for each geometrical shape, which is another big challenge in the molecular engineering of MOF materials. For example, more than 100 different topologies are possible for linking tetrahedral building blocks together into structures with just one kind of vertex (that is, all vertices related by symmetry), like diamond, the zeolite topologies, etc. Research reveals that only a small number of simple, high-symmetry structures will be expected to form most commonly. More complicated structures can be targeted by judicious use of appropriately shaped inorganic SBUs and linkers, and the consideration of effects of the solvent and template and reaction conditions [10], [16].

One of the most important objectives is the design of a third generation of molecular sieve, with large, regular, accessible cages and tunnels [17], [18]. There are many strategies to achieve large pores and high porosity. In this review, we will introduce three which are mainly considered from three important elements of MOF: topology of framework, inorganic metal centers, and organic ligands:

(1)
Synthesizing four-connected and porous MOFs with zeolite topology: by designing inorganic and organic four-connected nodes, the structures of MOFs with expanded zeolite topology would have larger pores and higher porosity than zeolites.
(2)
Synthesizing MOFs constructed from large metal clusters. Large metal clusters replace a vertex in a network, expanding the size of inorganic SBUs and the dimensions of the network, which leads to large pore size and high porosity.
(3)
Synthesizing MOFs with larger or longer organic linkers. Larger or longer organic ligands would expand the length of linker between inorganic SBU, benefitting large pore diameter and also high porosity just as metal clusters would. Owing to the maturity of organic synthesis, this strategy has proven to be more effective and easier to implement.

Although there are challenges in rational syntheses, MOFs allow systematic engineering of chemical and physical properties and structures through the choice and modifications of their components.

Section snippets

Synthetic methods of MOFs

The most traditional and commonly used crystal growth method is solvent evaporation by evaporating or cooling a saturated solution. A wide variety of other methods to obtain metal–organic frameworks have been explored, such as diffusion method, hydro(solvo)thermal method, microwave reaction and ultrasonic methods.

(1)
Solvent evaporation method. This technique needs convenient conditions: (a) crystals grow in saturated solutions; (b) solubility increases with temperature and crystals can appear

Multifunctional properties

As a new kind of porous material, MOFs manifest more attractive potential applications compared to traditional porous materials, which are mostly due to the possibilities for fine-tuning and modification of their pore structures and properties like pore dimensions, shapes, sizes, and pore surface properties. Most of MOFs have three-dimensional structures incorporating uniform pores and a network of channels. These pores and channels are often filled with terminal and guest species, usually

Conclusions

MOFs as a new member of porous materials have recently become a topic of central importance to inorganic and materials chemistry. In this review, we have provided molecular engineering for synthesis of MOFs and their potential applications. In the area of synthesis there are general methods, such as diffusion method, hydro(solvo)thermal method, microwave and ultrasonic methods, particularly the important factor of organic template in the reaction process. Meanwhile, we have described the

Acknowledgments

This work was funded by the State Basic Research Project (2006CB806100), Outstanding Young Scientist Foundation of NSFC (20625102), NSFC (Grant nos. 20831D02, 20571030, 20531030, and 20371020) and “111” program of Ministry of Education of China and Bureau of Science & Technology of Jilin Province, China and International Cooperation Project of Ministry of Science and Technology (2007DFA40830). The results reviewed here have of course been obtained thanks to the contribution of other scientists,

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In this research, a novel macrocyclic ligand was prepared by hydrogenation tetra aza macrocyclic and coupling with the 2-chloro-benzimidazole derivatives. The new metal-organic frameworks (MOFs) were synthesized by a reaction of Cu (II) ion with macrocyclic ligand (copper-macrocyclic organic framework (Cu-MMOFs)). The synthetic compound fully characterized by various analysis techniques. In electrochemical studies, Cu-MMOFs were employed as excellent modifiers on the surface glassy carbon electrode (GCE) with Nafion (NF) as (Cu-MMOFs/Nf/GCE) modified electrode to investigate the analytical performance of digoxin (DIG) with different electrochemical methods to clarify the electrocatalytic properties of DIG in phosphate buffer (PBS) solution. The diffusion coefficient (D_DIG = 1.38×10⁻⁶ cm² s⁻¹) and catalytic rate constant (k_cat = 0.287×10⁶ cm³ mol⁻¹ s⁻¹) were estimated for the oxidation of DIG at the surface of modified electrode. Under the optimal condition, the Cu-MMOFS/Nf/GCE displays a good electrochemical nature for DIG in the 0.019–38 μM range, with a low limit of detection (LOD) 0.0158 µM (S/N = 3) and a great reproducibility, repeatability and admirable selectivity. Additionally, the fabricated sensor exhibited excellent performance by measuring the concentration of DIG in real samples (such as human blood serum samples), which proves the potential of Cu-MMOFS/Nf/GCE for practical applicability with good favorable recoveries (100.35 %).
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Currently, the escalation of water pollution due to heavy metals has reached a critical point, posing a significant threat to human existence. Lead and its compounds, among these metals, exhibit notable stability, making them resistant to metabolic breakdown and degradation. However, the persistence of lead in water can endanger human well-being by infiltrating the food chain, leading to various ailments, including cancer. The adsorption approach has gained considerable prominence in the realm of heavy metal treatment methodologies, owing to its broad applicability, pronounced selectivity, and the potential for renewing and reusing adsorbents. Metal-organic frameworks (MOFs), characterized by their porous structure, have emerged as a premier choice for adsorbing heavy metal ions, thanks to their substantial specific surface area, robust stability, and minimal density. This comprehensive review aims to encapsulate and delve into the adsorption parameters, kinetics, and mechanisms inherent in the utilization of highly efficient and recyclable MOF composites for Pb(II) adsorption in water. This effort seeks to provide a foundational guide for prospective research endeavors and practical implementations.
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Exploring new frontiers in supercapacitor electrodes through MOF advancements
2024, Journal of Energy Storage
Supercapacitors (SCs) are considered remarkable energy storage technology because of their prolonged cycling longevity and power density (P_d). However, the constrained energy density (E_d) of SCs presents a notable barrier to their widespread adoption. Therefore, it is crucial to prioritize developing and exploring novel electrode materials to improve their electrochemical performance within SCs usage. The use of metal-organic frameworks (MOFs) in SCs has been subject to thorough investigation by researchers, primarily due to their noteworthy attributes, including but not limited to high porosity, customizable pore structure, and substantial specific surface area (SSA). The main objective of this review is to provide a compressive overview of the latest developments in the realm of pure MOFs and their associated composites, encompassing both MOF composites and MOF derivatives. Particular emphasis is placed on their utilization in the context of SCs applications. Furthermore, we provided individual viewpoints concerning the current challenges and prospective developments of these materials within the framework of SCs application.
New trends in metal-organic framework membranes for biomedical applications
2023, Materials Chemistry and Physics
Metal-organic framework (MOF) membranes are constructed with various organic ligands and metal ions or clusters. Due to their high porosity, tunable chemical composition, and potential for subsequent synthetic modifications, they are widely used in biomedicine, especially in biosensing, bioimaging, and drug delivery. Although MOF membranes have found many applications in various fields, including biomedicine, there are still fundamental gaps in studies on various aspects of such membranes. This lack of interest in the study of MOF membranes is because most researchers prefer to use bulk or powder MOFs because of the problematic aspects of fabricating perfect and defect-free MOF-based membranes. Therefore, in this review, applications of MOF membranes in nanomedicine are presented, focusing on their functions ranging from drug delivery, therapeutic agents for various diseases, and imaging contrast agents. Applications of MOF membrane derivatives in nanomedicine will also be presented. Finally, the challenges and prospects for MOF membranes in future applications will be highlighted.
A potential nonlinear optical material for crown-porphyrin complexes: Alkali metal doping and transition metal introducing
2023, Journal of Molecular Liquids
Crown ethers have inspired the rapid growth of research interest in the design and synthesis of functional materials due to their exceptional affinity for metal. In this work, a fascinating crown-porphyrin (Cr-Pr) complexes were studied with doping alkali metal (potassium, K atom) on the crown ether face and introducing transition metal (zinc, Zn atom) on the porphyrin face. The research reveals that the Cr-Pr complex with doped K and Zn atoms results in significant variations in nonlinear optical (NLO) properties. Interestingly, the crown ether ring with the K atom in the K@Cr-Pr complex leads to a remarkable first hyperpolarizability (β_tot). On the contrary, when introducing the Zn atom in porphyrins, the Cr-Pr@Zn complex exhibits no significant change in NLO response. Further, the combination of the K and Zn atoms in crown-porphyrin complex (K@Cr-Pr@Zn) can result in significant enhancement of their NLO characteristics, which is much greater than that of the K@Cr-Pr and the Cr-Pr@Zn complexes. The natural population analysis (NPA) and the molecular electrostatic potential maps (ESP) show that the doping of the K atom regulates effectively charge distribution in the complexes. Moreover, the great β_tot value can be further illustrated by their low transition energies and an obvious charge transfer (CT) transition in the main excited states. Therefore, the current work achieves that the NLO properties of crown ether derivatives can be regulated by doping alkali metals in the crown ether ring and provides a theoretical guide for developing high-performance NLO devices.

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ReviewMolecular engineering for synthesizing novel structures of metal–organic frameworks with multifunctional properties

Abstract

Introduction

Section snippets

Synthetic methods of MOFs

Multifunctional properties

Conclusions

Acknowledgments

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Review
Molecular engineering for synthesizing novel structures of metal–organic frameworks with multifunctional properties