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

Anna Broto-Ribas; Claudia Vignatti; Alicia Jimenez-Almarza; Javier Luis-Barrera; Zahra Dolatkhah; Felipe Gándara; Inhar Imaz; Rubén Mas-Ballesté; José Alemán; Daniel Maspoch

doi:10.1007/s12274-020-2779-8

Nano Research 2021, 14(2): 458-465 https://doi.org/10.1007/s12274-020-2779-8

Research Article | Issue | Published: 15 April 2020

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

Show Author's Information Hide Author's Information Anna Broto-Ribas^{¹^,^§}, Claudia Vignatti^{¹^,^§}, Alicia Jimenez-Almarza^², Javier Luis-Barrera^³, Zahra Dolatkhah^², Felipe Gándara^⁴, Inhar Imaz^{¹^,}(

), Rubén Mas-Ballesté^{³^,⁵^,}(

), José Alemán^{²^,⁵^,}(

), Daniel Maspoch^{¹^,⁶^,}(

)

1Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC and The Barcelona Institute of Science and Technology, 08193 Barcelona, Spain

2Inorganic Chemistry Department, Módulo 7, Universidad Autónoma de Madrid, 28049 Madrid, Spain

3Organic Chemistry Department, Módulo 1, Universidad Autónoma de Madrid, 28049 Madrid, Spain

4Materials Science Factory, Instituto de Ciencia de Materiales de Madrid (ICMM), Consejo Superior de Investigaciones Científicas (CSIC), Calle Sor Juana Inés de la Cruz, 3, 28049 Madrid, Spain

5Institute for Advanced Research in Chemical Sciences (IAdChem), Campus Universidad Autónoma de Madrid, 28049 Madrid, Spain

6Institució Catalana de Recerca i Estudis Avançats (ICREA), 08100 Barcelona, Spain

^§ Anna Broto-Ribas and Claudia Vignatti contributed equally to this work.

Keywords:

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

Topics:

Metals Organic frameworks Organic polymers Organometallics Topology

Cite this article:

Broto-Ribas A, Vignatti C, Jimenez-Almarza A, et al. Heterogeneous catalysts with programmable topologies generated by reticulation of organocatalysts into metal-organic frameworks: The case of squaramide. Nano Research, 2021, 14(2): 458-465. https://doi.org/10.1007/s12274-020-2779-8

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Abstract Full text Electronic supplementary material About this article

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.

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

Show Author's information Hide Author's Information Anna Broto-Ribas^{¹^,^§}, Claudia Vignatti^{¹^,^§}, Alicia Jimenez-Almarza^², Javier Luis-Barrera^³, Zahra Dolatkhah^², Felipe Gándara^⁴, Inhar Imaz^{¹^,}(

), Rubén Mas-Ballesté^{³^,⁵^,}(

), José Alemán^{²^,⁵^,}(

), Daniel Maspoch^{¹^,⁶^,}(

)

1Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC and The Barcelona Institute of Science and Technology, 08193 Barcelona, Spain

2Inorganic Chemistry Department, Módulo 7, Universidad Autónoma de Madrid, 28049 Madrid, Spain

3Organic Chemistry Department, Módulo 1, Universidad Autónoma de Madrid, 28049 Madrid, Spain

4Materials Science Factory, Instituto de Ciencia de Materiales de Madrid (ICMM), Consejo Superior de Investigaciones Científicas (CSIC), Calle Sor Juana Inés de la Cruz, 3, 28049 Madrid, Spain

5Institute for Advanced Research in Chemical Sciences (IAdChem), Campus Universidad Autónoma de Madrid, 28049 Madrid, Spain

6Institució Catalana de Recerca i Estudis Avançats (ICREA), 08100 Barcelona, Spain

^§ Anna Broto-Ribas and Claudia Vignatti contributed equally to this work.

Abstract

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

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Acknowledgements

Publication history

Received: 20 January 2020

Revised: 15 March 2020

Accepted: 25 March 2020

Published: 15 April 2020

Issue date: February 2021

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Acknowledgements

This work was supported by the Spanish MINECO (projects RTI2018-095622-B-I00 and RTI2018-095038-B-I00), the Catalan AGAUR (project 2017 SGR 238), the ERC under the EU FP7 (ERC-Co 615954), European Union’s Horizon 2020 research and innovation program under grant agreement No. 685727, and European Structural Funds (S2018/NMT-4367). It was also funded by the CERCA Program/Generalitat de Catalunya. ICN2 is supported by the Severo Ochoa program from the Spanish MINECO (Grant No. SEV-2017-0706).