Heterogeneous catalysts with programmable topologies generated by reticulation of organocatalysts into metal-organic frameworks : The case of squaramide
Broto-Ribas, Anna (Institut Català de Nanociència i Nanotecnologia)
Vignatti Abellan, Claudia (Institut Català de Nanociència i Nanotecnologia)
Jiménez Almarza, Alicia (Universidad Autónoma de Madrid. Departamento de Química Inorgánica)
Luis-Barrera, Javier (Universidad Autónoma de Madrid. Departamento de Química Orgánica)
Dolatkhah, Zahra (Universidad Autónoma de Madrid. Departamento de Química Inorgánica)
Gándara, Felipe (Instituto de Ciencia de Materiales de Madrid)
Imaz, Inhar (Institut Català de Nanociència i Nanotecnologia)
Mas Balleste, Ruben (Universidad Autónoma de Madrid. Departamento de Química Orgánica)
Maspoch Comamala, Daniel (Institut Català de Nanociència i Nanotecnologia)

Date:	2020
Abstract:	A well-established strategy to synthesize heterogeneous, metal-organic framework (MOF) catalysts that exhibit nanoconfinement effects, and specific pores with highly-localized catalytic sites, is to use organic linkers containing organocatalytic centers. Here, we report that by combining this linker approach with reticular chemistry, and exploiting three-dimensioanl (3D) MOF-structural data from the Cambridge Structural Database, we have designed four heterogeneous MOF-based catalysts for standard organic transformations. These programmable MOFs are isoreticular versions of pcu IRMOF-16, fcu UiO-68 and pillared-pcu SNU-8X, the three most common topologies of MOFs built from the organic linker p,p'-terphenyldicarboxylic acid (tpdc). To synthesize the four squaramide-based MOFs, we designed and synthesized a linker, 4,4'-((3,4-dioxocyclobut-1-ene-1,2-diyl)bis(azanedyil))dibenzoic acid (Sq_tpdc), which is identical in directionality and length to tpdc but which contains organocatalytic squaramide centers. Squaramides were chosen because their immobilization into a framework enhances its reactivity and stability while avoiding any self-quenching phenomena. Therefore, the four MOFs share the same organocatalytic squaramide moiety, but confine it within distinct pore environments. We then evaluated these MOFs as heterogeneous H-bonding catalysts in organic transformations: a Friedel-Crafts alkylation and an epoxide ring-opening. Some of them exhibited good performance in both reactions but all showed distinct catalytic profiles that reflect their structural differences.
Grants:	Ministerio de Economía y Competitividad RTI2018-095038-B-I00 Ministerio de Economía y Competitividad RTI2018-095622-B-I00 Agència de Gestió d'Ajuts Universitaris i de Recerca 2017/SGR-238 European Commission 615954 European Commission 685727 Ministerio de Economía y Competitividad S2018/NMT-4367 Ministerio de Economía y Competitividad SEV-2017-0706
Rights:	Tots els drets reservats.
Language:	Anglès
Document:	Article ; recerca ; Versió acceptada per publicar
Subject:	Reticular chemistry ; Metal-organic frameworks ; H-bond catalysis ; Squaramide ; Friedel-Crafts ; Epoxide ring-opening
Published in:	Nano research, vol. 14 (April 2020) p. 458-465, ISSN 1998-0000

DOI: 10.1007/s12274-020-2779-8

Postprint 21 p, 984.0 KB

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Research literature > UAB research groups literature > Research Centres and Groups (research output) > Experimental sciences > Catalan Institute of Nanoscience and Nanotechnology (ICN2)
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