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)

Fecha:	2019
Resumen:	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.
Ayudas:	European Commission 615954 Ministerio de Economía y Competitividad SEV-2017-0706 Ministerio de Economía y Competitividad FJCI-2017-31598 Ministerio de Economía y Competitividad IJCI-2016-29802 Ministerio de Economía y Competitividad MAT2015-65354-C2-1-R Agència de Gestió d'Ajuts Universitaris i de Recerca 2014/SGR-80
Derechos:	Tots els drets reservats.
Lengua:	Anglès
Documento:	Article ; recerca ; Versió acceptada per publicar
Materia:	Chemical functionalization ; Chemical instability ; Co-ordination chemistries ; Covalent chemistry ; Covalent functionalizations ; Functional molecules ; Hydrophilic/hydrophobic ; Metal-organic polyhedron
Publicado en:	Journal of the American Chemical Society, Vol. 141, issue 9 (March 2019) , p. 4094-4102, ISSN 1520-5126

DOI: 10.1021/jacs.8b13593

Postprint 12 p, 1.5 MB

El registro aparece en las colecciones:
Documentos de investigación > Documentos de los grupos de investigación de la UAB > Centros y grupos de investigación (producción científica) > Ciencias > Institut Català de Nanociència i Nanotecnologia (ICN2)
Documentos de investigación > Documentos de los grupos de investigación de la UAB > Centros y grupos de investigación (producción científica) > Ciencias > El Sincrotrón ALBA
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