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Issue 41, 2018
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Post-synthetic modification of zirconium metal–organic frameworks by catalyst-free aza-Michael additions

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Abstract

The reactions of the zirconium MOF [Zr6O4(OH)4(bdc-NH2)6] (UiO-66-NH2, bdc-NH2 = 2-amino-1,4-benzenedicarboxylate) with the Michael acceptors acrylonitrile (CH2[double bond, length as m-dash]CHCN), acrylic acid (CH2[double bond, length as m-dash]CHCO2H), methyl acrylate (CH2[double bond, length as m-dash]CHCO2Me) and methyl vinyl ketone (CH2[double bond, length as m-dash]CHC(O)Me) led to post-synthetic modification of the MOF through C–N bond formation without loss of crystallinity. The reactions with acrylonitrile and acrylic acid go to completion, yielding [Zr6O4(OH)4(bdc-NHCH2CH2CN)6] (UiO-66-AN, 1) and [Zr6O4(OH)4(bdc-NHCH2CH2CO2H)6] (UiO-66-AA, 2) respectively, whereas those with methyl acrylate and methyl vinyl ketone are incomplete, yielding [Zr6O4(OH)4(bdc-NH2)0.66(bdc-NHCH2CH2CO2Me)5.34] (UiO-66-MA, 3) and [Zr6O4(OH)4(bdc-NH2)2.76(bdc-NHCH2CH2C(O)Me)3.24] (UiO-66-MVK, 4), respectively. The acrylonitrile-modified MOF UiO-66-AN undergoes further reaction with sodium azide in the presence of zinc(II) chloride in n-butanol to form the tetrazolate-modified MOF [Zr6O4(OH)4(bdc-NHCH2CH2CN)4.74(bdc-NHCH2CH2CN4H)1.26] (UiO-66-TZ, 5).

Graphical abstract: Post-synthetic modification of zirconium metal–organic frameworks by catalyst-free aza-Michael additions

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Publication details

The article was received on 13 Aug 2018, accepted on 19 Sep 2018 and first published on 26 Sep 2018


Article type: Paper
DOI: 10.1039/C8DT03312A
Citation: Dalton Trans., 2018,47, 14491-14496
  • Open access: Creative Commons BY-NC license
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    Post-synthetic modification of zirconium metal–organic frameworks by catalyst-free aza-Michael additions

    H. Amer Hamzah, T. S. Crickmore, D. Rixson and A. D. Burrows, Dalton Trans., 2018, 47, 14491
    DOI: 10.1039/C8DT03312A

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