Post-synthetic modification of zirconium metal-organic frameworks by catalyst-free aza-Michael additions

Harina Amer Hamzah; Tom S. Crickmore; Daniel Rixson; Andrew D. Burrows

doi:10.1039/c8dt03312a

Post-synthetic modification of zirconium metal-organic frameworks by catalyst-free aza-Michael additions

Harina Amer Hamzah, Tom S. Crickmore, Daniel Rixson, Andrew D. Burrows

University of Bath

Research output: Contribution to journal › Article › peer-review

19 Citations (SciVal)

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 (CH₂CHCN), acrylic acid (CH₂CHCO₂H), methyl acrylate (CH₂CHCO₂Me) and methyl vinyl ketone (CH₂CHC(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).

Original language	English
Pages (from-to)	14491-14496
Number of pages	6
Journal	Dalton Transactions
Volume	47
Issue number	41
DOIs	https://doi.org/10.1039/c8dt03312a
Publication status	Published - 7 Nov 2018

Bibliographical note

Publisher Copyright:
© 2018 The Royal Society of Chemistry.

ASJC Scopus subject areas

Inorganic Chemistry

Access to Document

10.1039/c8dt03312aLicence: CC BY-NC

Cite this

@article{87b7c82d82ce4820a8500471c61a7154,

title = "Post-synthetic modification of zirconium metal-organic frameworks by catalyst-free aza-Michael additions",

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 (CH2CHCN), acrylic acid (CH2CHCO2H), methyl acrylate (CH2CHCO2Me) and methyl vinyl ketone (CH2CHC(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).",

author = "{Amer Hamzah}, Harina and Crickmore, {Tom S.} and Daniel Rixson and Burrows, {Andrew D.}",

note = "Publisher Copyright: {\textcopyright} 2018 The Royal Society of Chemistry.",

year = "2018",

month = nov,

day = "7",

doi = "10.1039/c8dt03312a",

language = "English",

volume = "47",

pages = "14491--14496",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "41",

}

TY - JOUR

T1 - Post-synthetic modification of zirconium metal-organic frameworks by catalyst-free aza-Michael additions

AU - Amer Hamzah, Harina

AU - Crickmore, Tom S.

AU - Rixson, Daniel

AU - Burrows, Andrew D.

PY - 2018/11/7

Y1 - 2018/11/7

N2 - 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 (CH2CHCN), acrylic acid (CH2CHCO2H), methyl acrylate (CH2CHCO2Me) and methyl vinyl ketone (CH2CHC(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).

AB - 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 (CH2CHCN), acrylic acid (CH2CHCO2H), methyl acrylate (CH2CHCO2Me) and methyl vinyl ketone (CH2CHC(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).

UR - http://www.scopus.com/inward/record.url?scp=85055175213&partnerID=8YFLogxK

U2 - 10.1039/c8dt03312a

DO - 10.1039/c8dt03312a

M3 - Article

C2 - 30256351

AN - SCOPUS:85055175213

SN - 1477-9226

VL - 47

SP - 14491

EP - 14496

JO - Dalton Transactions

JF - Dalton Transactions

IS - 41

ER -

Post-synthetic modification of zirconium metal-organic frameworks by catalyst-free aza-Michael additions

Abstract

Bibliographical note

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this