AI Chat Paper
Note: Please note that the following content is generated by AMiner AI. SciOpen does not take any responsibility related to this content.
{{lang === 'zh_CN' ? '文章概述' : 'Summary'}}
{{lang === 'en_US' ? '中' : 'Eng'}}
Chat more with AI
Powered by AMiner. Clicking this button will take you away from SciOpen.
Home Nano Research Article
Article Link
Cite
EndNote(RIS) BibTeX
Collect
Submit Manuscript
Show Outline
Outline
Show full outline
Hide outline
Outline
Show full outline
Hide outline
Research Article

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

Anna Broto-Ribas1,§, Claudia Vignatti1,§, Alicia Jimenez-Almarza2, Javier Luis-Barrera3, Zahra Dolatkhah2, Felipe Gándara4, Inhar Imaz1( ), Rubén Mas-Ballesté3,5( ), José Alemán2,5( ), Daniel Maspoch1,6( )
Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC and The Barcelona Institute of Science and Technology, 08193 Barcelona, Spain
Inorganic Chemistry Department, Módulo 7, Universidad Autónoma de Madrid, 28049 Madrid, Spain
Organic Chemistry Department, Módulo 1, Universidad Autónoma de Madrid, 28049 Madrid, Spain
Materials 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
Institute for Advanced Research in Chemical Sciences (IAdChem), Campus Universidad Autónoma de Madrid, 28049 Madrid, Spain
Institució Catalana de Recerca i Estudis Avançats (ICREA), 08100 Barcelona, Spain

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

Show Author Information

Graphical Abstract

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.

Keywords

reticular chemistrymetal-organic frameworksH-bond catalysissquaramideFriedel-Craftsepoxide ring-opening

Electronic Supplementary Material

Download File(s)
12274_2020_2779_MOESM1_ESM.pdf (2.9 MB)
12274_2020_2779_MOESM2_ESM.cif (4.2 MB)
12274_2020_2779_MOESM3_ESM.cif (2.2 MB)
12274_2020_2779_MOESM4_ESM.cif (3.4 MB)
12274_2020_2779_MOESM5_ESM.cif (1.6 MB)
12274_2020_2779_MOESM6_ESM.cif (2.5 MB)
12274_2020_2779_MOESM7_ESM.cif (4.2 MB)

References

[1]
Y. B. Huang,; J. Liang,; X. S. Wang,; R. Cao, Multifunctional metal-organic framework catalysts: Synergistic catalysis and tandem reactions. Chem. Soc. Rev. 2017, 46, 126-157.
Crossref Google Scholar
[2]
A. Dhakshinamoorthy,; Z. H. Li,; H. Garcia, Catalysis and photocatalysis by metal organic frameworks. Chem. Soc. Rev. 2018, 47, 8134-8172.
Crossref Google Scholar
[3]
J. W. Liu,; L. F. Chen,; H. Cui,; J. Y. Zhang,; L. Zhang,; C. Y. Y. Su, Applications of metal-organic frameworks in heterogeneous supramolecular catalysis. Chem. Soc. Rev. 2014, 43, 6011-6061.
Crossref Google Scholar
[4]
Y. B. Huang,; Z. J. Lin,; R. Cao, Palladium nanoparticles encapsulated in a metal-organic framework as efficient heterogeneous catalysts for direct C2 arylation of indoles. Chem.—Eur. J. 2011, 17, 12706-12712.
Crossref Google Scholar
[5]
Y. B. Huang,; Q. Wang,; J. Liang,; X. S. Wang,; R. Cao, Soluble metal-nanoparticle-decorated porous coordination polymers for the homogenization of heterogeneous catalysis. J. Am. Chem. Soc. 2016, 138, 10104-10107.
Crossref Google Scholar
[6]
J. V. Alegre-Requena,; E. Marqués-López,; R. P. Herrera,; D. D. Díaz, Metal-organic frameworks (MOFs) bring new life to hydrogen-bonding organocatalysts in confined spaces. CrystEngComm 2016, 18, 3985-3995.
Crossref Google Scholar
[7]
P. C. Rao,; S. Mandal, Potential utilization of metal-organic frameworks in heterogeneous catalysis: A case study of hydrogen-bond donating and single-site catalysis. Chem.—Asian J. 2019, 14, 4087-4102.
Crossref Google Scholar
[8]
X. W. Dong,; T. Liu,; Y. Z. Hu,; X. Y. Liu,; C. M. Che, Urea postmodified in a metal-organic framework as a catalytically active hydrogen-bond-donating heterogeneous catalyst. Chem. Commun. 2013, 49, 7681-7683.
Crossref Google Scholar
[9]
Y. Luan,; N. N. Zheng,; Y. Qi,; J. Tang,; G. Wang, Merging metal-organic framework catalysis with organocatalysis: A thiourea functionalized heterogeneous catalyst at the nanoscale. Catal. Sci. Technol. 2014, 4, 925-929.
Crossref Google Scholar
[10]
S. J. Garibay,; Z. Q. Wang,; S. M. Cohen, Evaluation of heterogeneous metal-organic framework organocatalysts prepared by postsynthetic modification. Inorg. Chem. 2010, 49, 8086-8091.
Crossref Google Scholar
[11]
Y. D. Zang,; J. Shi,; F. M. Zhang,; Y. J. Zhong,; W. D. Zhu, Sulfonic acid-functionalized MIL-101 as a highly recyclable catalyst for esterification. Catal. Sci. Technol. 2013, 3, 2044-2049.
Google Scholar
[12]
S. Aguado,; J. Canivet,; Y. Schuurman,; D. Farrusseng, Tuning the activity by controlling the wettability of MOF eggshell catalysts: A quantitative structure-activity study. J. Catal. 2011, 284, 207-214.
Google Scholar
[13]
X. P. Zhang,; Z. J. Zhang,; J. Boissonnault,; S. M. Cohen, Design and synthesis of squaramide-based MOFs as efficient MOF-supported hydrogen-bonding organocatalysts. Chem. Commun. 2016, 52, 8585-8588.
Google Scholar
[14]
S. M. Cohen,; Z. J. Zhang,; J. A. Boissonnault, Toward “metalloMOFzymes”: Metal-organic frameworks with single-site metal catalysts for small-molecule transformations. Inorg. Chem. 2016, 55, 7281-7290.
Google Scholar
[15]
A. A. Tehrani,; S. Abedi,; A. Morsali,; J. Wang,; P. C. Junk, Urea-containing metal-organic frameworks as heterogeneous organocatalysts. J. Mater. Chem. A 2015, 3, 20408-20415.
Google Scholar
[16]
P. C. Rao,; S. Mandal, Friedel-Crafts alkylation of indoles with nitroalkenes through hydrogen-bond-donating metal-organic framework. ChemCatChem 2017, 9, 1172-1176.
Google Scholar
[17]
E. A. Hall,; L. R. Redfern,; M. H. Wang,; K. A. Scheidt, Lewis acid activation of a hydrogen bond donor metal-organic framework for catalysis. ACS Catal. 2016, 6, 3248-3252.
Google Scholar
[18]
D. Markad,; S. K. Mandal, Design of a primary-amide-functionalized highly efficient and recyclable hydrogen-bond-donating heterogeneous catalyst for the Friedel-Crafts alkylation of indoles with β-nitrostyrenes. ACS Catal. 2019, 9, 3165-3173.
Google Scholar
[19]
Z. F. Ju,; S. C. Yan,; D. Q. Yuan, De novo tailoring pore morphologies and sizes for different substrates in a urea-containing MOFs catalytic platform. Chem. Mater. 2016, 28, 2000-2010.
Google Scholar
[20]
H. Zhang,; X. W. Gao,; L. Wang,; X. S. Zhao,; Q. Y. Li,; X. J. Wang, Microwave-assisted synthesis of urea-containing zirconium metal-organic frameworks for heterogeneous catalysis of Henry reactions. CrystEngComm 2019, 21, 1358-1362.
Google Scholar
[21]
X. J. Wang,; J. Li,; Q. Y. Li,; P. Z. Li,; H. Lu,; Q. Y. Lao,; R. Ni,; Y. H. Shi,; Y. L. Zhao, A urea decorated (3,24)-connected rht-type metal-organic framework exhibiting high gas uptake capability and catalytic activity. CrystEngComm 2015, 17, 4632-4636.
Google Scholar
[22]
P. Serra-Crespo,; E. V. Ramos-Fernandez,; J. Gascon,; F. Kapteijn, Synthesis and characterization of an amino functionalized MIL-101(Al): Separation and catalytic properties. Chem. Mater. 2011, 23, 2565-2572.
Google Scholar
[23]
P. W. Siu,; Z. J. Brown,; O. K. Farha,; J. T. Hupp,; K. A. Scheidt, A mixed dicarboxylate strut approach to enhancing catalytic activity of a de novo urea derivative of metal-organic framework UiO-67. Chem. Commun. 2013, 49, 10920-10922.
Google Scholar
[24]
J. M. Roberts,; B. M. Fini,; A. A. Sarjeant,; O. K. Farha,; J. T. Hupp,; K. A. Scheidt, Urea metal-organic frameworks as effective and size-selective hydrogen-bond catalysts. J. Am. Chem. Soc. 2012, 134, 3334-3337.
Google Scholar
[25]
C. M. McGuirk,; M. J. Katz,; C. L. Stern,; A. A. Sarjeant,; J. T. Hupp,; O. K. Farha,; C. A. Mirkin, Turning on catalysis: Incorporation of a hydrogen-bond-donating squaramide moiety into a Zr metal-organic framework. J. Am. Chem. Soc. 2015, 137, 919-925.
Google Scholar
[26]
D. J. Lun,; G. I. N. Waterhouse,; S. G. Telfer, A general thermolabile protecting group strategy for organocatalytic metal-organic frameworks. J. Am. Chem. Soc. 2011, 133, 5806-5809.
Google Scholar
[27]
C. Vignatti,; J. Luis-Barrera,; V. Guillerm,; I. Imaz,; R. Mas-Ballesté,; J. Alemán,; D. Maspoch, Squaramide-IRMOF-16 analogue for catalysis of solvent-free, epoxide ring-opening tandem and multicomponent reactions. ChemCatChem 2018, 10, 3995-3998.
Google Scholar
[28]
J. Liang,; R. P. Chen,; X. Y. Wang,; T. T. Liu,; X. S. Wang,; Y. B. Huang,; R. Cao, Postsynthetic ionization of an imidazole-containing metal-organic framework for the cycloaddition of carbon dioxide and epoxides. Chem. Sci. 2017, 8, 1570-1575.
Google Scholar
[29]
O. M. Yaghi, Reticular chemistry in all dimensions. ACS Cent. Sci. 2019, 5, 1295-1300.
Google Scholar
[30]
O. M. Yaghi, Reticular chemistry: Molecular precision in infinite 2D and 3D. Mol. Front. J. 2019, 3, 66-83.
Google Scholar
[31]
C. R. Groom,; I. J Bruno,; M. P. Lightfoot,; S. C. Ward, The Cambridge structural database. Acta Crystallogr. B Struct. Sci. Cryst. Eng. Mater. 2016, B72, 171-179.
Google Scholar
[32]
R. I. Storer,; C. Aciro,; L. H. Jones, Squaramides: Physical properties, synthesis and applications. Chem. Soc. Rev. 2011, 40, 2330-2346.
Google Scholar
[33]
J. Juanhuix,; F. Gil-Ortiz,; G. Cuni,; C. Colldelram,; J. Nicolás,; J. Lidón,; E. Boter,; C. Ruget,; S. Ferrer,; J. Benach, Developments in optics and performance at BL13-XALOC, the macromolecular crystallography beamline at the Alba Synchrotron. J. Synchrotron Radiat. 2014, 21, 679-689.
Google Scholar
[34]
W. Kabsch, XDS. Acta Crystallogr. Sect. D 2010, 66, 125-132.
Google Scholar
[35]
G. Sheldrick, SHELXT—Integrated space-group and crystal-structure determination. Acta Crystallogr. Sect. A. 2015, 71, 3-8.
Google Scholar
[36]
O. V. Dolomanov,; L. J. Bourhis,; R. J. Gildea,; J. A. K. Howard,; H. Puschmann, OLEX2: A complete structure solution, refinement and analysis program. J. Appl. Cryst. 2009, 42, 339-341.
Google Scholar
[37]
A. L. Spek, PLATON/SQUEEZE. Acta Cryst. 2020, E76, 1-11
Google Scholar
[38]
K. Manna,; P. F Ji,; Z. K. Lin,; F. X. Greene,; A. Urban,; N. C. Thacker,; W. B. Lin, Chemoselective single-site Earth-abundant metal catalysts at metal-organic framework nodes. Nat. Commun. 2016, 7, 12610.
Google Scholar
[39]
A. Schaate,; P. Roy,; A. Godt; J. Lippke,; F. Waltz,; M. Wiebcke,; P. Behrens, Modulated synthesis of Zr-based metal-organic frameworks: From Nano to single crystals. Chem.—Eur. J. 2011, 17, 6643-6651.
Google Scholar
[40]
M. Eddaoudi,; J. Kim,; N. Rosi,; D. Vodak,; J. Wachter,; M. O'Keeffe,; O. M. Yaghi, Systematic design of pore size and functionality in isoreticular MOFs and their application in methane storage. Science 2002, 295, 469-472.
Google Scholar
[41]
M. Carboni,; Z. K. Lin,; C. W. Abney,; T. Zhang,; W. B. Lin, A metal-organic framework containing unusual eight-connected Zr-oxo secondary building units and orthogonal carboxylic acids for ultra-sensitive metal detection. Chem.—Eur. J. 2014, 20, 14965-14970.
Google Scholar
[42]
Y. A. Li,; S. Yang,; Q. Y. Li,; J. P. Ma,, S. J. Zhang,; Y. B. Dong, UiO-68-ol NMOF-based fluorescent sensor for selective detection of HClO and its application in bioimaging. Inorg. Chem. 2017, 56, 13241-13248.
Google Scholar
[43]
K. Manna,; T. Zhang,; M. Carboni,; C. W. Abney,; W. B. Lin, Salicylaldimine-based metal-organic framework enabling highly active olefin hydrogenation with iron and cobalt catalysts. J. Am. Chem. Soc. 2014, 136, 13182-13185.
Google Scholar
[44]
E. A. Dolgopolova,; O. A. Ejegbavwo,; C. R. Martin,; M. D. Smith,; W. Setyawan,; S. G. Karakalos,; C. H. Henager,; H. C. Z. Loye,; N. B. Shustova, Multifaceted modularity: A key for stepwise building of hierarchical complexity in actinide metal-organic frameworks. J. Am. Chem. Soc. 2017, 139, 16852-16861.
Google Scholar
[45]
Y. He,; Y. L. Hou,; Y. L. Wong,; R. Xiao,; M. Q. Li,; Z. Hao,; J. Huang,; L. Wang,; M. Zeller,; J. He, Improving stability against desolvation and mercury removal performance of Zr(IV)-carboxylate frameworks by using bulky sulfur functions. J. Mater. Chem. A 2018, 6, 1648-1654.
Google Scholar
[46]
B. J. Li,; B. Gui,; G. P. Hu,; D. Q. Yuan,; C. Wang, Postsynthetic modification of an alkyne-tagged zirconium metal-organic framework via a “click” reaction. Inorg. Chem. 2015, 54, 5139-5141.
Google Scholar
[47]
H. B. Huang,; H. Sato,; T. Aida, Crystalline nanochannels with pendant azobenzene groups: Steric or polar effects on gas adsorption and diffusion? J. Am. Chem. Soc. 2017, 139, 8784-8787.
Google Scholar
[48]
G. E. M. Schukraft,; S. Ayala, Jr.; B. L. Dick,; S. M. Cohen, Isoreticular expansion of polyMOFs achieves high surface area materials. Chem. Commun. 2017, 53, 10684-10687.
Google Scholar
[49]
H. L. Jiang,; D. W. Feng,; T. F. Liu,; J. R. Li,; H. C. Zhou, Pore surface engineering with controlled loadings of functional groups via click chemistry in highly stable metal-organic frameworks. J. Am. Chem. Soc. 2012, 134, 14690-14693.
Google Scholar
[50]
B. Gui,; X. S. Meng,; Y. Chen,; J. W. Tian,; G. L. Liu,; C. C. Shen,; M. Zeller,; D. Q. Yuan,; C. Wang, Reversible tuning hydroquinone/ quinone reaction in metal-organic framework: Immobilized molecular switches in solid state. Chem. Mater. 2015, 27, 6426-6431.
Google Scholar
[51]
T. Y. Luo,; C. Liu,; S. V. Eliseeva,; P. F. Muldoon,; S. Petoud,; N. L. Rosi, Rare earth pcu metal-organic framework platform based on RE4(μ3-OH)4(COO)62+ clusters: Rational design, directed synthesis, and deliberate tuning of excitation wavelengths. J. Am. Chem. Soc. 2017, 139, 9333-9340.
Google Scholar
[52]
R. M. Wang,; M. H. Zhang,; X. B. Liu,; L. L. Zhang,; Z. X. Kang,; W. Wang,; X. Q. Wang,; F. N. Dai,; D. F. Sun, Tuning the dimensionality of interpenetration in a pair of framework-catenation isomers to achieve selective adsorption of CO2 and fluorescent sensing of metal ions. Inorg. Chem. 2015, 54, 6084-6086.
Google Scholar
[53]
K. Oisaki,; Q. W. Li,; H. Furukawa,; A. U. Czaja,; O. M. Yaghi, A metal-organic framework with covalently bound organometallic complexes. J. Am. Chem. Soc. 2010, 132, 9262-9264.
Google Scholar
[54]
L. Liu,; X. J. Wang,; Q. Zhang,; Q. W. Li,; Y. L. Zhao, Distinct interpenetrated metal-organic frameworks constructed from crown ether-based strut analogue. CrystEngComm 2013, 13, 841-844.
Google Scholar
[55]
C. L. Zhang,; H. Hao,; Z. Z. Shi,; H. G. Zheng, Four new metal-organic frameworks based on a rigid linear ligand: Synthesis, optical properties and structural investigation. CrystEngComm 2014, 16, 5662-5671.
Google Scholar
[56]
J. Sahu,; M. Ahmad,; P. K. Bharadwaj, Structural diversity and luminescence properties of coordination polymers built with a rigid linear dicarboxylate and Zn(II)/Pb(II) ion. Cryst. Growth Des. 2013, 13, 2618-2627.
Google Scholar
[57]
T. K. Prasad,; M. P. Suh, Metal-organic frameworks incorporating various alkoxy pendant groups: Hollow tubular morphologies, X-ray single-crystal structures, and selective carbon dioxide adsorption properties. Chem.—Asian J. 2015, 10, 2257-2263.
Google Scholar
[58]
I. M. Hauptvogel,; R. Biedermann,; N. Klein,; I. Senkovska,; A. Cadiau,; D. Wallacher,; R. Feyerherm,; S. Kaskel, Flexible and hydrophobic Zn-based metal-organic framework. Inorg. Chem. 2011, 50, 8367-8374.
Google Scholar
[59]
J. Sahu,; A. Aijaz,; Q. Xu,; P. K. Bharadwaj, A three-dimensional pillared-layer metal-organic framework: Synthesis, structure and gas adsorption studies. Inorg. Chim. Acta 2015, 430, 193-198.
Google Scholar
[60]
R. Singh,; P. K. Bharadwaj, Coordination polymers built with a linear bis-imidazole and different dicarboxylates: Unusual entanglement and emission properties. Cryst. Growth Des. 2013, 13, 3722-3733.
Google Scholar
[61]
G. Dutta,; A. K. Jana,; D. K. Singh,; M. Eswaramoorthy,; S. Natarajan, Encapsulation of silver nanoparticles in an amine-functionalized porphyrin metal-organic framework and its use as a heterogeneous catalyst for CO2 fixation under atmospheric pressure. Chem.—Asian J. 2018, 13, 2677-2684.
Google Scholar
[62]
X. Y. Liu,; B. Liu,; G. H. Li,; Y. L. Liu, Two anthracene-based metal-organic frameworks for highly effective photodegradation and luminescent detection in water. J. Mater. Chem. A 2018, 6, 17177-17185.
Google Scholar
[63]
D. W. Feng,; K. C. Wang,; Z. W. Wei,, Y. P. Chen,; C. M. Simon,; R. K. Arvapally,; R. L. Martin,; M. Bosch,; T. F. Liu,; S. Fordham, et al. Kinetically tuned dimensional augmentation as a versatile synthetic route towards robust metal-organic frameworks. Nat. Commun. 2014, 5, 5723.
Google Scholar
Nano Research
Volume 14 Issue 2,
February 2021
Pages 458-465
DOI: 10.1007/s12274-020-2779-8
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
Topics:
MetalsOrganic frameworks Organic polymersOrganometallicsTopology

780

Views

13

Crossref

N/A

Web of Science

10

Scopus

0

CSCD

Altmetrics
Received: 20 January 2020
Revised: 15 March 2020
Accepted: 25 March 2020
Published: 15 April 2020
© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature
Return