Investigating the chemical sensitivity of melting in zeolitic imidazolate frameworks

Alice M. Bumstead; Michael F. Thorne; Adam F. Sapnik; Celia Castillo-Blas; Giulio I. Lampronti; Thomas D. Bennett

doi:10.1039/d2dt02142k

Investigating the chemical sensitivity of melting in zeolitic imidazolate frameworks

Alice M. Bumstead, Michael F. Thorne, Adam F. Sapnik, Celia Castillo-Blas, Giulio I. Lampronti, Thomas D. Bennett^*

^*Corresponding author af dette arbejde

Kemisk Institut

Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › peer review

6 Citationer (Scopus)

3 Downloads (Pure)

Abstract

The number of zeolitic imidazolate frameworks (ZIFs) that form melt-quenched glasses remains limited, with most displaying the cag network topology. Here, we expand our studies to zni topology ZIFs, starting with ZIF-zni [Zn(Im)₂] before changing its linker chemistry, by incorporating 2-methylimidazolate and 5-aminobenzimidazolate. ZIF-zni was found to melt and form a glass, with T_m = 576 °C and T_g = 322 °C, although it was not possible to prepare the glass without zinc oxide impurities. The addition of 2-methylimidazolate to the structure gave ZIF-61 [Zn(Im)_1.35(mIm)_0.65], which decomposed without passing through the liquid state. However, incorporating small quantities of 5-aminobenzimidazolate resulted in a ZIF [Zn(Im)_1.995(abIm)_0.005] with a lower melting temperature (T_m = 569 °C) than pure ZIF-zni, and no evidence of zinc oxide growth. This demonstrates the sensitivity of melting behaviour in ZIFs towards linker chemistry, with only a 0.25% variation capable of eliciting a 7 °C change in melting temperature. This study highlights the chemical sensitivity of melting in ZIFs and serves as a promising strategy for tuning their melting behaviour.

Originalsprog	Engelsk
Tidsskrift	Dalton Transactions
Vol/bind	51
Udgave nummer	36
Sider (fra-til)	13636-13645
Antal sider	10
ISSN	1477-9226
DOI	https://doi.org/10.1039/d2dt02142k
Status	Udgivet - 19 aug. 2022

Bibliografisk note

Publisher Copyright:
© 2022 The Royal Society of Chemistry.

Adgang til dokumentet

10.1039/d2dt02142kLicens: CC BY

FulltextForlagets udgivne version, 1,26 MBLicens: CC BY

Citationsformater

@article{aa904a4313394fd1bd10fa957d0a3593,

title = "Investigating the chemical sensitivity of melting in zeolitic imidazolate frameworks",

abstract = "The number of zeolitic imidazolate frameworks (ZIFs) that form melt-quenched glasses remains limited, with most displaying the cag network topology. Here, we expand our studies to zni topology ZIFs, starting with ZIF-zni [Zn(Im)2] before changing its linker chemistry, by incorporating 2-methylimidazolate and 5-aminobenzimidazolate. ZIF-zni was found to melt and form a glass, with Tm = 576 °C and Tg = 322 °C, although it was not possible to prepare the glass without zinc oxide impurities. The addition of 2-methylimidazolate to the structure gave ZIF-61 [Zn(Im)1.35(mIm)0.65], which decomposed without passing through the liquid state. However, incorporating small quantities of 5-aminobenzimidazolate resulted in a ZIF [Zn(Im)1.995(abIm)0.005] with a lower melting temperature (Tm = 569 °C) than pure ZIF-zni, and no evidence of zinc oxide growth. This demonstrates the sensitivity of melting behaviour in ZIFs towards linker chemistry, with only a 0.25% variation capable of eliciting a 7 °C change in melting temperature. This study highlights the chemical sensitivity of melting in ZIFs and serves as a promising strategy for tuning their melting behaviour.",

author = "Bumstead, {Alice M.} and Thorne, {Michael F.} and Sapnik, {Adam F.} and Celia Castillo-Blas and Lampronti, {Giulio I.} and Bennett, {Thomas D.}",

note = "Funding Information: A.M.B. acknowledges the Royal Society for funding (RGF\EA\180092) and the Cambridge Trust for a Vice Chancellor's Award (304253100). M.F.T. thanks Corning Incorporated for PhD funding. A.F.S. acknowledges the EPSRC for a PhD studentship under the industrial CASE scheme along with Johnson Matthey PLC (JM11106). T.D.B. thanks the Royal Society for both a University Research Fellowship (URF\R\211013) and a research grant (RGS\R2\212221). T.D.B. also gratefully acknowledges the EPSRC (EP/R015481/1). T.D.B. also thanks the Leverhulme Trust for a Philip Leverhulme Prize and T.D.B. and C.C.B. also gratefully acknowledge funding by a Leverhulme Trust Research Project Grant (RPG-2020-005). We extend our thanks to Andrew Mason and Duncan Howe for collection of all H NMR spectra at the Yusuf Hamied Department of Chemistry, University of Cambridge. We also acknowledge both Dr Chris Ashling and Dr Remo Widmer for useful discussions. 1 Publisher Copyright: {\textcopyright} 2022 The Royal Society of Chemistry.",

year = "2022",

month = aug,

day = "19",

doi = "10.1039/d2dt02142k",

language = "English",

volume = "51",

pages = "13636--13645",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "36",

}

TY - JOUR

T1 - Investigating the chemical sensitivity of melting in zeolitic imidazolate frameworks

AU - Bumstead, Alice M.

AU - Thorne, Michael F.

AU - Sapnik, Adam F.

AU - Castillo-Blas, Celia

AU - Lampronti, Giulio I.

AU - Bennett, Thomas D.

N1 - Funding Information: A.M.B. acknowledges the Royal Society for funding (RGF\EA\180092) and the Cambridge Trust for a Vice Chancellor's Award (304253100). M.F.T. thanks Corning Incorporated for PhD funding. A.F.S. acknowledges the EPSRC for a PhD studentship under the industrial CASE scheme along with Johnson Matthey PLC (JM11106). T.D.B. thanks the Royal Society for both a University Research Fellowship (URF\R\211013) and a research grant (RGS\R2\212221). T.D.B. also gratefully acknowledges the EPSRC (EP/R015481/1). T.D.B. also thanks the Leverhulme Trust for a Philip Leverhulme Prize and T.D.B. and C.C.B. also gratefully acknowledge funding by a Leverhulme Trust Research Project Grant (RPG-2020-005). We extend our thanks to Andrew Mason and Duncan Howe for collection of all H NMR spectra at the Yusuf Hamied Department of Chemistry, University of Cambridge. We also acknowledge both Dr Chris Ashling and Dr Remo Widmer for useful discussions. 1 Publisher Copyright: © 2022 The Royal Society of Chemistry.

PY - 2022/8/19

Y1 - 2022/8/19

N2 - The number of zeolitic imidazolate frameworks (ZIFs) that form melt-quenched glasses remains limited, with most displaying the cag network topology. Here, we expand our studies to zni topology ZIFs, starting with ZIF-zni [Zn(Im)2] before changing its linker chemistry, by incorporating 2-methylimidazolate and 5-aminobenzimidazolate. ZIF-zni was found to melt and form a glass, with Tm = 576 °C and Tg = 322 °C, although it was not possible to prepare the glass without zinc oxide impurities. The addition of 2-methylimidazolate to the structure gave ZIF-61 [Zn(Im)1.35(mIm)0.65], which decomposed without passing through the liquid state. However, incorporating small quantities of 5-aminobenzimidazolate resulted in a ZIF [Zn(Im)1.995(abIm)0.005] with a lower melting temperature (Tm = 569 °C) than pure ZIF-zni, and no evidence of zinc oxide growth. This demonstrates the sensitivity of melting behaviour in ZIFs towards linker chemistry, with only a 0.25% variation capable of eliciting a 7 °C change in melting temperature. This study highlights the chemical sensitivity of melting in ZIFs and serves as a promising strategy for tuning their melting behaviour.

AB - The number of zeolitic imidazolate frameworks (ZIFs) that form melt-quenched glasses remains limited, with most displaying the cag network topology. Here, we expand our studies to zni topology ZIFs, starting with ZIF-zni [Zn(Im)2] before changing its linker chemistry, by incorporating 2-methylimidazolate and 5-aminobenzimidazolate. ZIF-zni was found to melt and form a glass, with Tm = 576 °C and Tg = 322 °C, although it was not possible to prepare the glass without zinc oxide impurities. The addition of 2-methylimidazolate to the structure gave ZIF-61 [Zn(Im)1.35(mIm)0.65], which decomposed without passing through the liquid state. However, incorporating small quantities of 5-aminobenzimidazolate resulted in a ZIF [Zn(Im)1.995(abIm)0.005] with a lower melting temperature (Tm = 569 °C) than pure ZIF-zni, and no evidence of zinc oxide growth. This demonstrates the sensitivity of melting behaviour in ZIFs towards linker chemistry, with only a 0.25% variation capable of eliciting a 7 °C change in melting temperature. This study highlights the chemical sensitivity of melting in ZIFs and serves as a promising strategy for tuning their melting behaviour.

U2 - 10.1039/d2dt02142k

DO - 10.1039/d2dt02142k

M3 - Journal article

C2 - 36039615

AN - SCOPUS:85138219669

SN - 1477-9226

VL - 51

SP - 13636

EP - 13645

JO - Dalton Transactions

JF - Dalton Transactions

IS - 36

ER -