Home > Articles > Published articles > Heterogeneous catalysts with programmable topologies generated by reticulation of organocatalysts into metal-organic frameworks : |
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 |
Postprint 21 p, 984.0 KB |