Stepwise synthesis of cubic heteroleptic metal-organic cages with Ruthenium(II)
(2025) KEMP20 20251Department of Chemistry
- Abstract
- The synthesis of metal-organic porous complexes within supramolecular chemistry is a topic of great interest due to their versatile use, e.g., molecular storage, sensors, drug delivery, molecular extractors, catalysis, and enzyme mimics, with applications in various fields such as bio-, agricultural-, and pharmaceutical chemistry. This is possible because smaller molecules enter the macromolecule complex and by host-guest interactions the aforementioned utilizations are possible, where the efficiency is determined by the smaller molecule’s pore accessibility to the cavities of the metal-organic structure. In general, these complexes are divided into two groups, one being MOFs (metal-organic frameworks) and the other MOCs (metal-organic... (More)
- The synthesis of metal-organic porous complexes within supramolecular chemistry is a topic of great interest due to their versatile use, e.g., molecular storage, sensors, drug delivery, molecular extractors, catalysis, and enzyme mimics, with applications in various fields such as bio-, agricultural-, and pharmaceutical chemistry. This is possible because smaller molecules enter the macromolecule complex and by host-guest interactions the aforementioned utilizations are possible, where the efficiency is determined by the smaller molecule’s pore accessibility to the cavities of the metal-organic structure. In general, these complexes are divided into two groups, one being MOFs (metal-organic frameworks) and the other MOCs (metal-organic cages). The main difference between these two groups is that MOFs are polymeric complexes that are built continuously as long as material exists, whereas MOCs do not polymerize. In general, the smallest unit of a MOF is a MOC, and due to these characteristics, the pore accessibility of MOFs and MOCs are significantly different, where the latter with higher pore accessibility is superior when it comes to functional use.
The majority of the reported MOC structures are homoleptic; however, the interest in synthesizing heteroleptic MOCs is on the rise due to their higher functionality, which is caused by the improved host-guest interactions resulting in a higher affinity. A problem is the complexity in assembling heteroleptic MOCs in comparison to homoleptic ones due to the complex strategies that require substantial knowledge about the properties of the metal and organic linker ligand. There are various methods to assemble heteroleptic MOCs, although they result in either a robust or controlled product, thus with the current methods there is no known way to synthesize heteroleptic MOCs in an effective way that yields both a controlled and robust product.
The objective of this work is to investigate a synthesis method to stepwise assemble a heteroleptic cubic MOC, using ruthenium(II) as metal-anchor and three different organic linker ligands. This work is a continuation of a master thesis recently published, and the highlight of the present study is the successful assembling of the bridging complexes, in addition to further characterizations of the intermediates, ligands, and complexes. (Less) - Popular Abstract
- Metal-organic framework (MOF) and cages (MOC) are supramolecular porous structures composed of metals connected by organic linkers ligands and is a topic that has sparked great interest in various fields of chemistry during the past few decades. The structures are usually synthesized by self-assembly reactions and results in three-dimensional geometrical structures such as squares, triangles, diamonds, and lanterns. The porous structure interacts with smaller molecules allowing for versatile functions, where common uses are as molecular storage, chemical sensing, and drug transport. However, in recent years the potential to use these structures as enzyme mimics or chemical extractors that allow for the storage of big compounds such as... (More)
- Metal-organic framework (MOF) and cages (MOC) are supramolecular porous structures composed of metals connected by organic linkers ligands and is a topic that has sparked great interest in various fields of chemistry during the past few decades. The structures are usually synthesized by self-assembly reactions and results in three-dimensional geometrical structures such as squares, triangles, diamonds, and lanterns. The porous structure interacts with smaller molecules allowing for versatile functions, where common uses are as molecular storage, chemical sensing, and drug transport. However, in recent years the potential to use these structures as enzyme mimics or chemical extractors that allow for the storage of big compounds such as heavy metal or nuclear waste has also been discussed. To improve the interactions between the metal-organic porous structure and the target molecule it is significantly more beneficial to use various organic linkers, making the structure heteroleptic. The majority of MOFs and MOCs are homoleptic (same organic linker), thus limiting their functions. Synthesis of heteroleptic structures requires complex strategies that typically yield either robust or controlled products; thus, achieving both these properties are not simple.
In this work we continue to investigate and propose a new synthetic strategy to stepwise assemble specifically heteroleptic cubic MOC in a both controlled and robust fashion, using ruthenium as metal anchor and three (out of four) organic linker ligands. If the method proves successful, then it will significantly contribute to the future of MOC synthesis studies. (Less)
Please use this url to cite or link to this publication:
http://lup.lub.lu.se/student-papers/record/9208609
- author
- Larsson, George LU
- supervisor
- organization
- course
- KEMP20 20251
- year
- 2025
- type
- L3 - Miscellaneous, Projetcs etc.
- subject
- keywords
- Metal-Organic Cage, framework, Self-assembly, Ruthenium
- language
- English
- id
- 9208609
- date added to LUP
- 2025-08-27 08:53:20
- date last changed
- 2025-08-27 08:53:20
@misc{9208609,
abstract = {{The synthesis of metal-organic porous complexes within supramolecular chemistry is a topic of great interest due to their versatile use, e.g., molecular storage, sensors, drug delivery, molecular extractors, catalysis, and enzyme mimics, with applications in various fields such as bio-, agricultural-, and pharmaceutical chemistry. This is possible because smaller molecules enter the macromolecule complex and by host-guest interactions the aforementioned utilizations are possible, where the efficiency is determined by the smaller molecule’s pore accessibility to the cavities of the metal-organic structure. In general, these complexes are divided into two groups, one being MOFs (metal-organic frameworks) and the other MOCs (metal-organic cages). The main difference between these two groups is that MOFs are polymeric complexes that are built continuously as long as material exists, whereas MOCs do not polymerize. In general, the smallest unit of a MOF is a MOC, and due to these characteristics, the pore accessibility of MOFs and MOCs are significantly different, where the latter with higher pore accessibility is superior when it comes to functional use.
The majority of the reported MOC structures are homoleptic; however, the interest in synthesizing heteroleptic MOCs is on the rise due to their higher functionality, which is caused by the improved host-guest interactions resulting in a higher affinity. A problem is the complexity in assembling heteroleptic MOCs in comparison to homoleptic ones due to the complex strategies that require substantial knowledge about the properties of the metal and organic linker ligand. There are various methods to assemble heteroleptic MOCs, although they result in either a robust or controlled product, thus with the current methods there is no known way to synthesize heteroleptic MOCs in an effective way that yields both a controlled and robust product.
The objective of this work is to investigate a synthesis method to stepwise assemble a heteroleptic cubic MOC, using ruthenium(II) as metal-anchor and three different organic linker ligands. This work is a continuation of a master thesis recently published, and the highlight of the present study is the successful assembling of the bridging complexes, in addition to further characterizations of the intermediates, ligands, and complexes.}},
author = {{Larsson, George}},
language = {{eng}},
note = {{Student Paper}},
title = {{Stepwise synthesis of cubic heteroleptic metal-organic cages with Ruthenium(II)}},
year = {{2025}},
}