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Postsynthetic covalent and coordination functionalization of rhodium(II)-based metal-organic polyhedra
Carné Sánchez, Arnau (Institut Català de Nanociència i Nanotecnologia)
Albalad, Jorge (Institut Català de Nanociència i Nanotecnologia)
Grancha, Thais (Institut Català de Nanociència i Nanotecnologia)
Imaz, Inhar (Institut Català de Nanociència i Nanotecnologia)
Juanhuix, Judith (ALBA Laboratori de Llum de Sincrotró)
Larpent, Patrick (Kyoto University. Institute for Integrated Cell-Material Science)
Furukawa, Shuhei (Kyoto University. Department of Synthetic Chemistry and Biological Chemistry)
Maspoch Comamala, Daniel (Institut Català de Nanociència i Nanotecnologia)

Date: 2019
Abstract: Metal-organic polyhedra (MOP) are ultrasmall (typically 1-4 nm) porous coordination cages made from the self-assembly of metal ions and organic linkers and are amenable to the chemical functionalization of its periphery; however, it has been challenging to implement postsynthetic functionalization due to their chemical instability. Herein, we report the use of coordination chemistries and covalent chemistries to postsynthetically functionalize the external surface of â‰2. 5 nm stable Rh(II)-based cuboctahedra through their Rh-Rh paddlewheel units or organic linkers, respectively. We demonstrate that 12 N-donor ligands, including amino acids, can be coordinated on the periphery of Rh-MOPs. We used this reactivity to introduce new functionalities (e. g. , chirality) to the MOPs and to tune their hydrophilic/hydrophobic characteristics, which allowed us to modulate their solubility in diverse solvents such as dichloromethane and water. We also demonstrate that all 24 organic linkers can be postsynthetically functionalized with esters via covalent chemistry. In addition, we anticipate that these two types of postsynthetic reactions can be combined to yield doubly functionalized Rh-MOPs, in which a total of 36 new functional molecules can be incorporated on their surfaces. Likewise, these chemistries could be synergistically combined to enable covalent functionalization of MOPs through new linkages such as ethers. We believe that both reported postsynthetic pathways can potentially be used to engineer Rh-MOPs as scaffolds for applications in delivery, sorption, and catalysis.
Note: Número d'acord de subvenció EC/FP7/615954
Note: Número d'acord de subvenció MINECO/SEV-2017-0706
Note: Número d'acord de subvenció MINECO/FJCI-2017-31598
Note: Número d'acord de subvenció MINECO/IJCI-2016-29802
Note: Número d'acord de subvenció MINECO/MAT2015-65354-C2-1-R
Note: Número d'acord de subvenció AGAUR/2014/SGR-80
Rights: Tots els drets reservats.
Language: Anglès.
Document: article ; recerca ; acceptedVersion
Subject: Chemical functionalization ; Chemical instability ; Co-ordination chemistries ; Covalent chemistry ; Covalent functionalizations ; Functional molecules ; Hydrophilic/hydrophobic ; Metal-organic polyhedron
Published in: Journal of the American Chemical Society, Vol. 141, issue 9 (March 2019) , p. 4094-4102, ISSN 1520-5126

DOI: 10.1021/jacs.8b13593

12 p, 1.5 MB

The record appears in these collections:
Research literature > UAB research groups literature > Research Centres and Groups (scientific output) > Experimental sciences > Catalan Institute of Nanoscience and Nanotechnology (ICN2)
Articles > Research articles
Articles > Published articles

 Record created 2019-07-02, last modified 2020-05-25

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