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Nano Research

Article Title

Heterogeneous catalysts with programmable topologies generated by reticulation of organocatalysts into metal-organic frameworks: The case of squaramide

Authors

Anna Broto-Ribas, Catalan Institute of Nanoscience and Nanotechnology , CSIC and The Barcelona Institute of Science and Technology, 08193 Barcelona, Spain
Claudia Vignatti, Catalan Institute of Nanoscience and Nanotechnology , CSIC and The Barcelona Institute of Science and Technology, 08193 Barcelona, Spain
Alicia Jimenez-Almarza, Inorganic Chemistry Department, Módulo 7, Universidad Autónoma de Madrid, 28049 Madrid, Spain
Javier Luis-Barrera, Organic Chemistry Department, Módulo 1, Universidad Autónoma de Madrid, 28049 Madrid, Spain
Zahra Dolatkhah, Inorganic Chemistry Department, Módulo 7, Universidad Autónoma de Madrid, 28049 Madrid, Spain
Felipe Gándara, Materials Science Factory, Instituto de Ciencia de Materiales de Madrid , Consejo Superior de Investigaciones Científicas , Calle Sor Juana Inés de la Cruz, 3, 28049 Madrid, Spain
Inhar Imaz, Catalan Institute of Nanoscience and Nanotechnology , CSIC and The Barcelona Institute of Science and Technology, 08193 Barcelona, Spain
Rubén Mas-Ballesté, Organic Chemistry Department, Módulo 1, Universidad Autónoma de Madrid, 28049 Madrid, Spain;Institute for Advanced Research in Chemical Sciences , Campus Universidad Autónoma de Madrid, 28049 Madrid, Spain
José Alemán, Inorganic Chemistry Department, Módulo 7, Universidad Autónoma de Madrid, 28049 Madrid, Spain;Institute for Advanced Research in Chemical Sciences , Campus Universidad Autónoma de Madrid, 28049 Madrid, Spain
Daniel Maspoch, Catalan Institute of Nanoscience and Nanotechnology , CSIC and The Barcelona Institute of Science and Technology, 08193 Barcelona, Spain;Institució Catalana de Recerca i Estudis Avançats , 08100 Barcelona, Spain

Keywords

reticular chemistry, metal-organic frameworks, H-bond catalysis, squaramide, Friedel-Crafts, epoxide ring-opening

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.

Publisher

Tsinghua University Press

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