Metal-Organic Cages and Their Applications

A special issue of Chemistry (ISSN 2624-8549). This special issue belongs to the section "Supramolecular Chemistry".

Deadline for manuscript submissions: closed (30 September 2022) | Viewed by 16228

Special Issue Editor


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Guest Editor
Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, UK
Interests: supramolecular chemistry and self-assembly; coordination chemistry; metal–organic cages; host–guest chemistry; X-ray crystallography; materials chemistry

Special Issue Information

Dear colleagues,

Metal–organic cages, a class of molecular containers formed via coordination-driven self-assembly, have attracted significant interest, both due to their aesthetically attractive structures and appealing host–guest properties arising from their well-defined internal cavities. Such host molecules have potential applications ranging from sensing and drug delivery to the separation of a diverse range of industrially important substrates. They also enable the reactivities of guests to be modulated, allowing sensitive species to be protected from the environment and species to be transformed via inner-phase catalysis in a manner similar to enzymes in natural systems. Many of these applications have been explored with a limited number of cages and there is much scope for the design of new cages with targeted functions as well as the development of new applications for existing cages and their incorporation into functional materials. In this Special Issue of Chemistry, devoted to "Metal–Organic Cages and Their Applications", we warmly invite submissions related to the synthesis, characterisation and applications of this fascinating class of supramolecular architecture.

Kind regards,

Dr. Tanya Ronson
Guest Editor

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Keywords

  • metal-organic cages
  • host–guest chemistry
  • supramolecular chemistry
  • self-assembly
  • supramolecular coordination chemistry
  • supramolecular catalysis
  • supramolecular materials

Published Papers (5 papers)

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Research

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7 pages, 1891 KiB  
Communication
Virus-like Cage Hybrid: Covalent Organic Cages Attached to Metal Organic Cage
by Zhuoqian Lv, Chenjuan Yu, Xinyuan Zhu and Youfu Wang
Chemistry 2022, 4(3), 865-871; https://0-doi-org.brum.beds.ac.uk/10.3390/chemistry4030062 - 26 Aug 2022
Cited by 2 | Viewed by 1917
Abstract
A well-defined virus-like cage hybrid (VCH) with 24 covalent organic cages (COCs) attached to one metal organic cage (MOC) is presented here. The quantitative assembly of VCH was completed through coordination between soluble anisotropic COC bearing one bipyridine moiety and Pd(II) ions. The [...] Read more.
A well-defined virus-like cage hybrid (VCH) with 24 covalent organic cages (COCs) attached to one metal organic cage (MOC) is presented here. The quantitative assembly of VCH was completed through coordination between soluble anisotropic COC bearing one bipyridine moiety and Pd(II) ions. The obtained VCH exhibited discrete, uniform and stable structures with good solubility and was well characterized by NMR, FT-IR, TEM, AFM, DLS, TGA, and so on. This designable cage hybrid promotes a new strategy to expand the structural and functional complexities of porous molecular cages. Full article
(This article belongs to the Special Issue Metal-Organic Cages and Their Applications)
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13 pages, 3792 KiB  
Article
Self-Assembly of a Rare High Spin FeII/PdII Tetradecanuclear Cubic Cage Constructed via the Metalloligand Approach
by Hyunsung Min, Alexander R. Craze, Takahiro Taira, Matthew J. Wallis, Mohan M. Bhadbhade, Ruoming Tian, Daniel J. Fanna, Richard Wuhrer, Shinya Hayami, Jack K. Clegg, Christopher E. Marjo, Leonard F. Lindoy and Feng Li
Chemistry 2022, 4(2), 535-547; https://0-doi-org.brum.beds.ac.uk/10.3390/chemistry4020038 - 26 May 2022
Cited by 5 | Viewed by 3145
Abstract
Polynuclear heterobimetallic coordination cages in which different metal cations are connected within a ligand scaffold are known to adopt a variety of polyhedral architectures, many of which display interesting functions. Within the extensive array of coordination cages incorporating Fe(II) centres reported so far, [...] Read more.
Polynuclear heterobimetallic coordination cages in which different metal cations are connected within a ligand scaffold are known to adopt a variety of polyhedral architectures, many of which display interesting functions. Within the extensive array of coordination cages incorporating Fe(II) centres reported so far, the majority contain low-spin (LS) Fe(II), with high-spin (HS) Fe(II) being less common. Herein, we present the synthesis and characterisation of a new tetradecanuclear heterobimetallic [Fe8Pd6L8](BF4]28 (1) cubic cage utilising the metalloligand approach. Use of the tripodal tris-imidazolimine derivative (2) permitted the formation of the tripodal HS Fe(II) metalloligand [FeL](BF4)2·CH3OH (3) that was subsequently used to form the coordination cage 1. Magnetic and structural analyses gave insight into the manner in which the HS environment of the metalloligand was transferred into the cage architecture along with the structural changes that accompanied its occupancy of the eight corners of the discrete cubic structure. Full article
(This article belongs to the Special Issue Metal-Organic Cages and Their Applications)
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12 pages, 26486 KiB  
Article
A Family of Externally-Functionalised Coordination Cages
by Garrett D. Jackson, Max B. Tipping, Christopher G. P. Taylor, Jerico R. Piper, Callum Pritchard, Cristina Mozaceanu and Michael D. Ward
Chemistry 2021, 3(4), 1203-1214; https://0-doi-org.brum.beds.ac.uk/10.3390/chemistry3040088 - 14 Oct 2021
Cited by 8 | Viewed by 3109
Abstract
New synthetic routes are presented to derivatives of a (known) M8L12 cubic coordination cage in which a range of different substituents are attached at the C4 position of the pyridyl rings at either end of the bis(pyrazolyl-pyridine) bridging ligands. [...] Read more.
New synthetic routes are presented to derivatives of a (known) M8L12 cubic coordination cage in which a range of different substituents are attached at the C4 position of the pyridyl rings at either end of the bis(pyrazolyl-pyridine) bridging ligands. The substituents are (i) –CN groups (new ligand LCN), (ii) –CH2OCH2–CCH (containing a terminal alkyne) groups (new ligand LCC); and (iii) –(CH2OCH2)3CH2OMe (tri-ethyleneglycol monomethyl ether) groups (new ligand LPEG). The resulting functionalised ligands combine with M2+ ions (particularly Co2+, Ni2+, Cd2+) to give isostructural [M8L12]16+ cage cores bearing 24 external functional groups; the cages based on LCN (with M2+ = Cd2+) and LCC (with M2+ = Ni2+) have been crystallographically characterised. The value of these is twofold: (i) exterior nitrile or alkene substituents can provide a basis for further synthetic opportunities via ‘Click’ reactions allowing in principle a diverse range of functionalisation of the cage exterior surface; (ii) the exterior –(CH2OCH2)3CH2OMe groups substantially increase cage solubility in both water and in organic solvents, allowing binding constants of cavity-binding guests to be measured under an increased range of conditions. Full article
(This article belongs to the Special Issue Metal-Organic Cages and Their Applications)
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Review

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18 pages, 4412 KiB  
Review
Complementarity and Preorganisation in the Assembly of Heterometallic–Organic Cages via the Metalloligand Approach—Recent Advances
by Feng Li and Leonard F. Lindoy
Chemistry 2022, 4(4), 1439-1456; https://doi.org/10.3390/chemistry4040095 - 07 Nov 2022
Cited by 2 | Viewed by 1961
Abstract
The design of new metallocage polyhedra towards pre-determined structures can offer both practical as well as intellectual challenges. In this mini-review we discuss a selection of recent examples in which the use of the metalloligand approach has been employed to overcome such challenges. [...] Read more.
The design of new metallocage polyhedra towards pre-determined structures can offer both practical as well as intellectual challenges. In this mini-review we discuss a selection of recent examples in which the use of the metalloligand approach has been employed to overcome such challenges. An attractive feature of this approach is its stepwise nature that lends itself to the design and rational synthesis of heterometallic metal–organic cages, with the latter often associated with enhanced functionality. Full article
(This article belongs to the Special Issue Metal-Organic Cages and Their Applications)
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26 pages, 7274 KiB  
Review
Metal–Organic Cages: Applications in Organic Reactions
by Shangjun Chen and Li-Jun Chen
Chemistry 2022, 4(2), 494-519; https://0-doi-org.brum.beds.ac.uk/10.3390/chemistry4020036 - 18 May 2022
Cited by 11 | Viewed by 4691
Abstract
Supramolecular metal–organic cages, a class of molecular containers formed via coordination-driven self-assembly, have attracted sustained attention for their applications in catalysis, due to their structural aesthetics and unique properties. Their inherent confined cavity is considered to be analogous to the binding pocket of [...] Read more.
Supramolecular metal–organic cages, a class of molecular containers formed via coordination-driven self-assembly, have attracted sustained attention for their applications in catalysis, due to their structural aesthetics and unique properties. Their inherent confined cavity is considered to be analogous to the binding pocket of enzymes, and the facile tunability of building blocks offers a diverse platform for enzyme mimics to promote organic reactions. This minireview covers the recent progress of supramolecular metal–organic coordination cages for boosting organic reactions as reaction vessels or catalysts. The developments in the utilizations of the metal–organic cages for accelerating the organic reactions, improving the selectivity of the reactions are summarized. In addition, recent developments and successes in tandem or cascade reactions promoted by supramolecular metal–organic cages are discussed. Full article
(This article belongs to the Special Issue Metal-Organic Cages and Their Applications)
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