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A green route approach to the synthesis of Ni(II) and Zn(II) templated metal–organic frameworks

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Abstract

A new synthetic route involving mixing of solid reactants followed by heating has been developed for the preparation of two templated metal–organic frameworks (MOFs). [Ni(NO3)2(bipy)2](pyrene)2 (1) was obtained by mixing together Ni(NO3)2·6H2O, 4,4-bipyridine and pyrene followed by heating at 85 °C for 4 h, while [Zn2(fumarate)2(bipy)] (2) was synthesized by mixing together Zn(O2CCH3)2·2H2O, fumaric acid and 4,4-bipyridine followed by heating at 160 °C for 16 h. The materials were characterized by elemental analysis, FT-IR spectroscopy and X-ray powder diffraction analysis (XRPD). Comparison of XRPD patterns of the materials with patterns simulated from the single crystal X-ray diffraction data, obtained from Cambridge Structural database, allowed identification of the products. Conversion of solid reactants to MOFs occurs spontaneously even when reactants are not mechanically stressed. Overall, the study suggests that MOFs can be synthesized in solid state simply by mixing together appropriate reactants without co-mill (ball-mill). Compared with traditional synthetic techniques such as solvothermal, ball-milling and solution-based, this method is environmentally friendly and highly efficient in the manufacture of these MOFs on a large scale.

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References

  1. Anastas PT, Kirchhoff MM, Williamson TC (2001) Catalysis as a foundational pillar of green chemistry. Appl Catal A 221:3–13

    Article  Google Scholar 

  2. Adams CJ, Kurawa MA, Lusi M, Orphen AG (2008) Solid state synthesis of coordination compounds from basic metal salts. CrystEngCom 10:1790–1795

    Article  Google Scholar 

  3. Yang H, Orefuwa S, Goudy A (2011) Study of mechanochemical synthesis in the formation of the metal–organic framework Cu3(BTC)2 for hydrogen storage. Microporous Mesoporous Mater 143:37–45

    Article  Google Scholar 

  4. Yaghi OM, O’Keefe M, Ockwig NW, Chae HK, Eddaoudi M, Kim J (2003) Reticular synthesis and the design of new materials. Nature 423:705–714

    Article  Google Scholar 

  5. Seo YK, Hundal G, Jang IT, Hwang YK, Jung CH, Chang JS (2009) Microwave synthesis of hybrid inorganic–organic materials including porous Cu3(BTC)2 from Cu(II)-trimesate mixture. Microporous Mesoporous Mater 119:331–337

    Article  Google Scholar 

  6. Isaeva VI, Tsachenko OP, Bruera TR, Nissenbaum VD, Mushin IV, Grunert W, Kustov LM (2011) New metal organic framework structures based on 2,5-pyridinedicarboxylate ligands and Zn2+ ions. Russ J Phys Chem A 85:462–465

    Article  Google Scholar 

  7. Lii DT, Bozzuutto DJ, Cahii CL (2005) Templated metal–organic frameworks: synthesis, structures, thermal properties and solid-state transformation of two novel calcium–adipate frameworks. Dalton Trans 2111–2115

  8. Lee JY, Olson DH, Pan L, Emge TL, Li J (2007) Microporous metal–organic frameworks with high gas sorption and separation capacity. Adv Funct Mater 17:1255–1262

    Article  Google Scholar 

  9. Haque E, Khan NA, Park JH, Jhung SH (2010) Synthesis of a metal–organic framework material, iron terephthalate, by ultrasound, microwave, and conventional electric heating: a kinetic study. Chem Eur J 16:1046–1052

    Article  Google Scholar 

  10. Khan NA, Haque E, Jhung SH (2010) Rapid syntheses of a metal–organic framework material Cu3(BTC)2(H2O)3 under microwave: a quantitative analysis of accelerated syntheses. Phys Chem Chem Phys 12:2625–2631

    Article  Google Scholar 

  11. Pichon A, Garay AL, James SL (2006) Solvent-free synthesis of a microporous metal–organic framework. CrystEngComm 8:211–214

    Article  Google Scholar 

  12. Yuan W, Friscic T, Apperley D, James SL (2010) High reactivity of metal–organic frameworks under grinding conditions: parallels with organic molecular materials. Angew Chem Int Ed 49:3916–3919

    Article  Google Scholar 

  13. Pichon A, James SL (2008) An array-based study of reactivity under solvent-free mechanochemical conditions-insights and trends. CrystEngComm 10:1839–1847

    Article  Google Scholar 

  14. Yuan W, O’Conor J, James SL (2010) Mechanochemical synthesis of homo- and hetero-rare-earth(III) metal–organic frameworks by ball milling. CrystEngComm 12:3515–3517

    Article  Google Scholar 

  15. Fujii K, Garay AL, Hill J, Sbircea E, Pan Z, Xu M, Apperley DC, James SL, Harris KDM (2010) Direct structure elucidation by powder X-ray diffraction of a metal–organic framework material prepared by solvent-free grinding. Chem Commun 46:7572–7574

    Article  Google Scholar 

  16. Li Z-Q, Qui LG, Xu T, Wu Y, Wang W, Wu Z-Y, Jiang X (2009) Ultrasonic synthesis of the microporous metal–organic framework Cu3(BTC)2 at ambient temperature and pressure: an efficient and environmentally friendly method. Mater Lett 63:78–80

    Article  Google Scholar 

  17. Ma B-Q, Mulfort KL, Hupp JT (2005) Microporous pillared paddle-wheel frameworks based on mixed-ligand coordination of zinc ions. Inorg Chem 44:4912–4914

    Article  Google Scholar 

  18. Biradha K, Doniasevitch KV, Moulton B, Seward C, Zaworotko MJ (1999) Covalent and noncovalent interpenetrating planar networks in the crystal structure of {[Ni(4,4′-bipyridine)2(NO3)22pyrene) n . Chem Commun 1327–1328

  19. Biradha K, Mondal A, Moulton B, Zaworotko MJ (2000) Coexisting covalent and non-covalent planar networks in the crystal structures of {[M(bipy)2(NO3)2]·arene} n (M = Ni, 1; Co, 2; arene = chlorobenzene, o-dichlorobenzene, benzene, nitrobenzene, toluene or anisole). Dalton Trans 3837–3844

  20. Suresh E, Boopalan K, Jasra RV, Bhadbhade MM (2001) Synthesis and single crystal investigation of two-dimensional rectangular network [M(4,4′-bpy)(Phth)(H2O)] n ·2H2O with small neutral cavities. Inorg Chem 40:4078–4080

    Article  Google Scholar 

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Acknowledgements

ACT is grateful to the Royal Society of Chemistry for the award of JWT Jones Fellowship and Professor Stuart James of Queen’s University Belfast, United Kingdom for the research facility.

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Authors and Affiliations

  1. Department of Chemistry, University of Ilorin, P.M.B. 1515, Ilorin, Nigeria

    Adedibu C. Tella & Samson O. Owalude

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  1. Adedibu C. Tella
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  2. Samson O. Owalude
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Correspondence to Adedibu C. Tella.

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Tella, A.C., Owalude, S.O. A green route approach to the synthesis of Ni(II) and Zn(II) templated metal–organic frameworks. J Mater Sci 49, 5635–5639 (2014). https://doi.org/10.1007/s10853-014-8277-1

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  • DOI: https://doi.org/10.1007/s10853-014-8277-1

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