Skip to content

Research at St Andrews

Nanoporous Carbohydrate Metal-Organic Frameworks

Research output: Contribution to journalArticlepeer-review

DOI

Author(s)

Ross S. Forgan, Ronald A. Smaldone, Jeremiah J. Gassensmith, Hiroyasu Furukawa, David B. Cordes, Qiaowei Li, Christopher E. Wilmer, Youssry Y. Botros, Randall Q. Snurr, Alexandra Martha Zoya Slawin, J. Fraser Stoddart

School/Research organisations

Abstract

The binding of alkali and alkaline earth metal cations by macrocyclic and diazamacrobicyclic polyethers, composed of ordered arrays of hard oxygen (and nitrogen) donor atoms, underpinned the development of host-guest supramolecular chemistry in the 1970s and 1980s. The arrangement of -OCCO- and -OCCN- chelating units in these preorganized receptors, including, but not limited to, crown ethers and cryptands, is responsible for the very high binding constants observed for their complexes with Group IA and IIA cations. The cyclodextrins (CDs), cyclic oligosaccharides derived microbiologically from starch, also display this -OCCO- bidentate motif on both their primary and secondary faces. The self-assembly, in aqueous alcohol, of infinite networks of extended structures, which have been termed CD-MOFs, wherein gamma-cyclodextrin (gamma-CD) is linked by coordination to Group IA and IIA metal cations to form metal-organic frameworks (MOFs), is reported. CD-MOF-1 and CD-MOF-2, prepared on the gram-scale from KOH and RbOH, respectively, form body-centered cubic arrangements of (gamma-CD)(6) cubes linked by eight-coordinate alkali metal cations. These cubic CD-MOFs are (i) stable to the removal of solvents, (ii) permanently porous, with surface areas of similar to 1200 m(2) g(-1), and (iii) capable of storing gases and small molecules within their pores. The fact that the -OCCO- moieties of gamma-CD are not prearranged in a manner conducive to encapsulating single metal cations has led to our isolating other infinite frameworks, with different topologies, from salts of Na+, Cs+, and Sr2+. This lack of preorganization is expressed emphatically in the case of Cs+, where two polymorphs assemble under identical conditions. CD-MOF-3 has the cubic topology observed for CD-MOFs 1 and 2, while CD-MOF-4 displays a channel structure wherein gamma-CD tori are perfectly stacked in one dimension in a manner reminiscent of the structures of some gamma-CD solvates, but with added crystal stability imparted by metal-ion coordination. These new MOFs demonstrate that the CDs can indeed function as ligands for alkali and alkaline earth metal cations in a manner similar to that found with crown ethers. These inexpensive, green, nanoporous materials exhibit absorption properties which make them realistic candidates for commercial development, not least of all because edible derivatives, fit for human consumption, can be prepared entirely from food-grade ingredients.

Close

Details

Original languageEnglish
Pages (from-to)406-417
Number of pages12
JournalJournal of the American Chemical Society
Volume134
Issue number1
DOIs
Publication statusPublished - 11 Jan 2012

Discover related content
Find related publications, people, projects and more using interactive charts.

View graph of relations

Related by author

  1. Solvothermal synthesis of a novel calcium metal-organic 2 framework: high temperature and electrochemical behaviour

    Main, R. M., Cordes, D. B., Desai, A. V., Slawin, A. M. Z., Wheatley, P., Armstrong, A. R. & Morris, R. E., 22 Nov 2021, In: Molecules. 26, 22, 7048.

    Research output: Contribution to journalArticlepeer-review

  2. Janus all-cis 2,3,4,5,6-pentafluorocyclohexyl building blocks applied to medicinal chemistry and bioactives discovery chemistry

    Clark, J., Neyyappadath, R. M., Yu, C., Slawin, A. M. Z., Cordes, D. B. & O'Hagan, D., 17 Nov 2021, In: Chemistry - A European Journal. 27, 64, p. 16000-16005 7 p., 202102819.

    Research output: Contribution to journalArticlepeer-review

  3. Scope, limitations and mechanistic analysis of the HyperBTM-catalyzed acylative kinetic resolution of tertiary heterocyclic alcohols

    Smith, S., Greenhalgh, M. D., Feoktistova, T., Walden, D. M., Taylor, J. E., Cordes, D. B., Slawin, A. M. Z., Cheong, P. H-Y. & Smith, A. D., 11 Nov 2021, (E-pub ahead of print) In: European Journal of Organic Chemistry. Early View

    Research output: Contribution to journalArticlepeer-review

  4. Simple and inexpensive method for the detection of carbon monoxide released from thermal cheletropic decarbonylation reactions

    Smellie, I., Carpenter-Warren, C. L., Chalmers, B. A., Cordes, D. B., Freire De Araujo Gouy, R. P., Keddie, N. S., Lebl, T., Patterson, I. L. J. & Slawin, A. M. Z., 9 Nov 2021, In: Journal of Chemical Education. 98, 11, p. 3608-3613

    Research output: Contribution to journalArticlepeer-review

  5. Substitution effects on a new pyridylbenzimidazole acceptor for thermally activated delayed fluorescence and their use in organic light-emitting diodes

    Hall, D., Rajamalli, P., Duda, E., Madayanad Suresh, S., Rodella, F., Bagnich, S., Carpenter-Warren, C. L., Cordes, D. B., Slawin, A. M. Z., Strohriegl, P., Beljonne, D., Köhler, A., Olivier, Y. & Zysman-Colman, E., 18 Oct 2021, In: Advanced Optical Materials. 9, 20, 13 p., 2100846.

    Research output: Contribution to journalArticlepeer-review

Related by journal

  1. Journal of the American Chemical Society (Journal)

    David Trevor Richens (Editor)

    2005 → …

    Activity: Publication peer-review and editorial work typesEditor of research journal

Related by journal

  1. Benchmark test and guidelines for DEER/PELDOR experiments on nitroxide-labeled biomolecules

    Schiemann, O., Heubach, C., Abdullin, D., Ackermann, K., Azarkh, M., Bagryanskaya, E., Drescher, M., Endeward, B., Freed, J., Galazzo, L., Goldfarb, D., Hett, T., Esteban Hofer, L., Fábregas Ibáñez, L., Hustedt, E., Kucher, S., Kuprov, I., Lovett, J. E., Meyer, A., Ruthstein, S. & 10 others, Saxena, S., Stoll, S., Timmel, C., Di Valentin, M., Mchaourab, H., Prisner, T., Bode, B. E., Bordignon, E., Bennati, M. & Jeschke, G., 19 Oct 2021, (E-pub ahead of print) In: Journal of the American Chemical Society. Articles ASAP, 16 p.

    Research output: Contribution to journalArticlepeer-review

  2. A molecular replication process drives supramolecular polymerization

    Feng, Y. & Philp, D., 7 Oct 2021, (E-pub ahead of print) In: Journal of the American Chemical Society. Articles ASAP

    Research output: Contribution to journalArticlepeer-review

  3. Difluorocarbene generation from TMSCF3: kinetics and mechanism of NaI-mediated and Si-induced anionic chain reactions

    García-Domínguez, A., West, T. H., Primozic, J. J., Grant, K. M., Johnston, C. P., Cumming, G. G., Leach, A. G. & Lloyd-Jones, G. C., 26 Aug 2020, In: Journal of the American Chemical Society. 142, 34, p. 14649-14663

    Research output: Contribution to journalArticlepeer-review

  4. Metal-ligand cooperation facilitates bond activation and catalytic hydrogenation with zinc pincer complexes

    Rauch, M., Kar, S., Kumar, A., Avram, L., Shimon, L. J. W. & Milstein, D., 26 Aug 2020, In: Journal of the American Chemical Society. 142, 34, p. 14513-14521

    Research output: Contribution to journalArticlepeer-review

  5. Hydrogenative depolymerization of nylons

    Kumar, A., von Wolff, N., Rauch, M., Zou, Y-Q., Shmul, G., Ben-David, Y., Leitus, G., Avram, L. & Milstein, D., 19 Aug 2020, In: Journal of the American Chemical Society. 142, 33, p. 14267-14275

    Research output: Contribution to journalArticlepeer-review

ID: 19890035

Top