scholarly journals Multifunctional Aromatic Carboxylic Acids as Versatile Building Blocks for Hydrothermal Design of Coordination Polymers

Crystals ◽  
2018 ◽  
Vol 8 (2) ◽  
pp. 83 ◽  
Author(s):  
Jinzhong Gu ◽  
Min Wen ◽  
Xiaoxiao Liang ◽  
Zifa Shi ◽  
Marina Kirillova ◽  
...  
Keyword(s):  
Carboxylic Acids ◽  
Coordination Polymers ◽  
Crystal Engineering ◽  
Building Blocks ◽  
Structural Features ◽  
Molar Ratio ◽  
Hydrothermal Conditions ◽  
Polycarboxylic Acids ◽  
Sensing Applications ◽  
Metal Organic

Selected recent examples of coordination polymers (CPs) or metal-organic frameworks (MOFs) constructed from different multifunctional carboxylic acids with phenyl-pyridine or biphenyl cores have been discussed. Despite being still little explored in crystal engineering research, such types of semi-rigid, thermally stable, multifunctional and versatile carboxylic acid building blocks have become very promising toward the hydrothermal synthesis of metal-organic architectures possessing distinct structural features, topologies, and functional properties. Thus, the main aim of this mini-review has been to motivate further research toward the synthesis and application of coordination polymers assembled from polycarboxylic acids with phenyl-pyridine or biphenyl cores. The importance of different reaction parameters and hydrothermal conditions on the generation and structural types of CPs or MOFs has also been highlighted. The influence of the type of main di- or tricarboxylate ligand, nature of metal node, stoichiometry and molar ratio of reagents, temperature, and presence of auxiliary ligands or templates has been showcased. Selected examples of highly porous or luminescent CPs, compounds with unusual magnetic properties, and frameworks for selective sensing applications have been described.

A threefold interpenetrated two-dimensional zinc(II) supramolecular architecture based on 3-nitrobenzoic acid and 4,4′-bipyridine

2016 ◽  
Vol 72 (2) ◽  
pp. 128-132 ◽  
Author(s):  
Long Tang ◽  
Ji-Jiang Wang ◽  
Feng Fu ◽  
Sheng-Wen Wang ◽  
Qi-Rui Liu
Keyword(s):  
Coordination Polymers ◽  
Crystal Engineering ◽  
Critical Factor ◽  
Building Blocks ◽  
Zigzag Chain ◽  
Great Success ◽  
Supramolecular Architecture ◽  
Two Dimensional ◽  
Hydrothermal Conditions ◽  
Nitrobenzoic Acid

With regard to crystal engineering, building block or modular assembly methodologies have shown great success in the design and construction of metal–organic coordination polymers. The critical factor for the construction of coordination polymers is the rational choice of the organic building blocks and the metal centre. The reaction of Zn(OAc)2·2H2O (OAc is acetate) with 3-nitrobenzoic acid (HNBA) and 4,4′-bipyridine (4,4′-bipy) under hydrothermal conditions produced a two-dimensional zinc(II) supramolecular architecture,catena-poly[[bis(3-nitrobenzoato-κ2O,O′)zinc(II)]-μ-4,4′-bipyridine-κ2N:N′], [Zn(C7H4NO4)2(C10H8N2)]nor [Zn(NBA)2(4,4′-bipy)]n, which was characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis and single-crystal X-ray diffraction analysis. The ZnIIions are connected by the 4,4′-bipy ligands to form a one-dimensional zigzag chain and the chains are decorated with anionic NBA ligands which interact further through aromatic π–π stacking interactions, expanding the structure into a threefold interpenetrated two-dimensional supramolecular architecture. The solid-state fluorescence analysis indicates a slight blue shift compared with pure 4,4′-bipyridine and HNBA.

Crystal engineering on superpolyhedral building blocks in metal–organic frameworks applied in gas adsorption

2015 ◽  
Vol 71 (6) ◽  
pp. 613-618 ◽  
Author(s):  
Ying-Pin Chen ◽  
Tian-Fu Liu ◽  
Stephen Fordham ◽  
Hong-Cai Zhou
Keyword(s):  
Surface Area ◽  
Crystal Engineering ◽  
Gas Adsorption ◽  
Metal Organic Frameworks ◽  
Supercritical Drying ◽  
Building Blocks ◽  
Structural Features ◽  
Open Channels ◽  
Bet Surface Area ◽  
Metal Organic

Two metal–organic frameworks [PCN-426(Ni) and PCN-427(Cu)] have been designed and synthesized to investigate the structure predictability using a SBB (supermolecular building blocks) approach. Tetratopic ligands featuring 120° angular carboxylate moieties were coordinated with a [Ni3(μ3-O)] cluster and a [Cu2O2] unit, respectively. As topologically predicted, 4-connected networks with square coordination adopted the nbo net for the Ni-MOF and ssb net for the Cu-MOF. PCN-426(Ni) was augmented with 12-connected octahedral SBBs, while PCN-427(Cu) was constructed with tetragonal open channels. After a CO2 supercritical drying procedure, the PCN-426(Ni) possessed a Brunauer–Emmett–Teller (BET) surface area as high as 3935 m2 g−1 and impressively high N2 uptake of 1500 cm3 g−1. This work demonstrates the generalization of the SBB strategy, finding an alternative to inconvenient synthetic processes to achieve the desired structural features.

Novel double layer lanthanide metal–organic networks for sensing applications

2018 ◽  
Vol 47 (2) ◽  
pp. 465-474 ◽  
Author(s):  
Jun Wang ◽  
Qiang-Sheng Zhang ◽  
Wei Dou ◽  
Alexander M. Kirillov ◽  
Wei-Sheng Liu ◽  
...  
Keyword(s):  
Double Layer ◽  
Coordination Polymers ◽  
Hydrothermal Conditions ◽  
Sensing Applications ◽  
Metal Organic ◽  
Lanthanide Metal ◽  
Organic Networks

Two isostructural lanthanide-based 2D coordination polymers were synthesized under hydrothermal conditions and fully characterized. The obtained compounds display notable sensing ability for p-phenylenediamine, benzidine, and acetone analytes.

scholarly journals Inverse Design of Nanoporous Crystalline Reticular Materials with Deep Generative Models

2020 ◽  
Author(s):  
Zhenpeng Yao ◽  
Benjamin Sanchez-Lengeling ◽  
N. Scott Bobbitt ◽  
Benjamin J. Bucior ◽  
Sai Govind Hari Kumar ◽  
...  
Keyword(s):  
Self Assembly ◽  
Metal Organic Framework ◽  
Internal Surface ◽  
Building Blocks ◽  
Structural Features ◽  
Generative Models ◽  
Combinatorial Design ◽  
Surface Areas ◽  
Molecular Building Blocks ◽  
Metal Organic

Reticular frameworks are crystalline porous materials that form <i>via</i> the self-assembly of molecular building blocks (<i>i.e.</i>, nodes and linkers) in different topologies. Many of them have high internal surface areas and other desirable properties for gas storage, separation, and other applications. The notable variety of the possible building blocks and the diverse ways they can be assembled endow reticular frameworks with a near-infinite combinatorial design space, making reticular chemistry both promising and challenging for prospective materials design. Here, we propose an automated nanoporous materials discovery platform powered by a supramolecular variational autoencoder (SmVAE) for the generative design of reticular materials with desired functions. We demonstrate the automated design process with a class of metal-organic framework (MOF) structures and the goal of separating CO<sub>2</sub> from natural gas or flue gas. Our model exhibits high fidelity in capturing structural features and reconstructing MOF structures. We show that the autoencoder has a promising optimization capability when jointly trained with multiple top adsorbent candidates identified for superior gas separation. MOFs discovered here are strongly competitive against some of the best-performing MOFs/zeolites ever reported. This platform lays the groundwork for the design of reticular frameworks for desired applications.

scholarly journals Investigation of the Preparation and Reactivity of Metal-Organic Frameworks of Cerium and Pyridine-2,4,6-Tricarboxylate

2021 ◽  
Author(s):  
Juliana Fonseca de Lima ◽  
Fernanda V.S. Moreno ◽  
Bruno A.T. Menezes ◽  
Jader da Silva Barbosa ◽  
Matthew C. Waddington ◽  
...  
Keyword(s):  
Coordination Polymers ◽  
Metal Organic Frameworks ◽  
Hydrothermal Conditions ◽  
Metal Organic

The synthesis of three coordination polymers of cerium(III) and the ligand pyridine-2,4,6-tricarboxylate (PTC) is reported. Two of the materials crystallise under hydrothermal conditions at 180 °C, with [Ce(PTC)(H2O)2]·1.5H2O, (1), being...

scholarly journals Inverse Design of Nanoporous Crystalline Reticular Materials with Deep Generative Models

2020 ◽  
Author(s):  
Zhenpeng Yao ◽  
Benjamin Sanchez-Lengeling ◽  
N. Scott Bobbitt ◽  
Benjamin J. Bucior ◽  
Sai Govind Hari Kumar ◽  
...  
Keyword(s):  
Self Assembly ◽  
Metal Organic Framework ◽  
Internal Surface ◽  
Building Blocks ◽  
Structural Features ◽  
Generative Models ◽  
Combinatorial Design ◽  
Surface Areas ◽  
Molecular Building Blocks ◽  
Metal Organic

Reticular frameworks are crystalline porous materials that form <i>via</i> the self-assembly of molecular building blocks (<i>i.e.</i>, nodes and linkers) in different topologies. Many of them have high internal surface areas and other desirable properties for gas storage, separation, and other applications. The notable variety of the possible building blocks and the diverse ways they can be assembled endow reticular frameworks with a near-infinite combinatorial design space, making reticular chemistry both promising and challenging for prospective materials design. Here, we propose an automated nanoporous materials discovery platform powered by a supramolecular variational autoencoder (SmVAE) for the generative design of reticular materials with desired functions. We demonstrate the automated design process with a class of metal-organic framework (MOF) structures and the goal of separating CO<sub>2</sub> from natural gas or flue gas. Our model exhibits high fidelity in capturing structural features and reconstructing MOF structures. We show that the autoencoder has a promising optimization capability when jointly trained with multiple top adsorbent candidates identified for superior gas separation. MOFs discovered here are strongly competitive against some of the best-performing MOFs/zeolites ever reported. This platform lays the groundwork for the design of reticular frameworks for desired applications.

scholarly journals Inverse Design of Nanoporous Crystalline Reticular Materials with Deep Generative Models

2020 ◽  
Author(s):  
Zhenpeng Yao ◽  
Benjamin Sanchez-Lengeling ◽  
N. Scott Bobbitt ◽  
Benjamin J. Bucior ◽  
Sai Govind Hari Kumar ◽  
...  
Keyword(s):  
Self Assembly ◽  
Metal Organic Framework ◽  
Internal Surface ◽  
Building Blocks ◽  
Structural Features ◽  
Generative Models ◽  
Combinatorial Design ◽  
Surface Areas ◽  
Molecular Building Blocks ◽  
Metal Organic

Reticular frameworks are crystalline porous materials that form <i>via</i> the self-assembly of molecular building blocks (<i>i.e.</i>, nodes and linkers) in different topologies. Many of them have high internal surface areas and other desirable properties for gas storage, separation, and other applications. The notable variety of the possible building blocks and the diverse ways they can be assembled endow reticular frameworks with a near-infinite combinatorial design space, making reticular chemistry both promising and challenging for prospective materials design. Here, we propose an automated nanoporous materials discovery platform powered by a supramolecular variational autoencoder (SmVAE) for the generative design of reticular materials with desired functions. We demonstrate the automated design process with a class of metal-organic framework (MOF) structures and the goal of separating CO<sub>2</sub> from natural gas or flue gas. Our model exhibits high fidelity in capturing structural features and reconstructing MOF structures. We show that the autoencoder has a promising optimization capability when jointly trained with multiple top adsorbent candidates identified for superior gas separation. MOFs discovered here are strongly competitive against some of the best-performing MOFs/zeolites ever reported. This platform lays the groundwork for the design of reticular frameworks for desired applications.

scholarly journals Chemistry of porous coordination polymers

2007 ◽  
Vol 79 (12) ◽  
pp. 2155-2177 ◽  
Author(s):  
Tapas Kumar Maji ◽  
Susumu Kitagawa
Keyword(s):  
Coordination Polymers ◽  
Metal Ion ◽  
Activated Carbons ◽  
Building Blocks ◽  
Point Of View ◽  
Central Metal ◽  
Materials Chemistry ◽  
Organic Hybrid ◽  
Potential Applications ◽  
Metal Organic

Remarkable advances in the recent development of porous compounds based upon coordination polymers have paved the way toward functional chemistry having potential applications such as gas storage, separation, and catalysis. From the synthetic point of view, the advantage is a designable framework, which can readily be constructed from building blocks, the so-called bottom-up assembly. Compared with conventional porous materials such as zeolites and activated carbons, porous inorganic-organic hybrid frameworks have higher potential for adsorption of small molecules because of their designability with respect to the coordination geometry around the central metal ion as well as size and probable multifunctionality of bridging organic ligands. Although rigidity and robustness of porous framework with different degree of adsorption are the most studied properties of metal-organic coordination frameworks, there are few studies on dynamic porous frameworks, which could open up a new dimension in materials chemistry.

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