TY - JOUR
T1 - Microporosity of a Guanidinium Organodisulfonate Hydrogen-Bonded Framework
AU - Brekalo, Ivana
AU - Deliz, David E.
AU - Barbour, Leonard J.
AU - Ward, Michael D.
AU - Friščić, Tomislav
AU - Holman, K. Travis
N1 - Funding Information:
This work was supported by the NSF (DMR-1610882). I.B. acknowledges support from GU (Kunin Fellowship), the ICDD (Ludo Frevel Scholarship), and the IUCr (travel grant). We thank Prof. M. Garcia-Garibay for suggesting the study of G2BDS, and Drs. S. Lapidus and N. Henderson for help with collecting the synchrotron PXRD data and with PXRD structure solution. Use of the Advanced Photon Source at Argonne National Laboratory was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357.
Publisher Copyright:
© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2020/1/27
Y1 - 2020/1/27
N2 - Guanidinium organosulfonates (GSs) are a large and well-explored archetypal family of hydrogen-bonded organic host frameworks that have, over the past 25 years, been regarded as nonporous. Reported here is the only example to date of a conventionally microporous GS host phase, namely guanidinium 1,4-benzenedisulfonate (p-G2BDS). p-G2BDS is obtained from its acetone solvate, AcMe@G2BDS, by single-crystal-to-single-crystal (SC-SC) desolvation, and exhibits a Type I low-temperature/pressure N2 sorption isotherm (SABET=408.7(2) m2 g−1, 77 K). SC-SC sorption of N2, CO2, Xe, and AcMe by p-G2BDS is explored under various conditions and X-ray diffraction provides a measurement of the high-pressure, room temperature Xe and CO2 sorption isotherms. Though p-G2BDS is formally metastable relative to the “collapsed”, nonporous polymorph, np-G2BDS, a sample of p-G2BDS survived for almost two decades under ambient conditions. np-G2BDS reverts to zCO2@p-G2BDS or yXe@p-G2BDS (y,z=variable) when pressure of CO2 or Xe, respectively, is applied.
AB - Guanidinium organosulfonates (GSs) are a large and well-explored archetypal family of hydrogen-bonded organic host frameworks that have, over the past 25 years, been regarded as nonporous. Reported here is the only example to date of a conventionally microporous GS host phase, namely guanidinium 1,4-benzenedisulfonate (p-G2BDS). p-G2BDS is obtained from its acetone solvate, AcMe@G2BDS, by single-crystal-to-single-crystal (SC-SC) desolvation, and exhibits a Type I low-temperature/pressure N2 sorption isotherm (SABET=408.7(2) m2 g−1, 77 K). SC-SC sorption of N2, CO2, Xe, and AcMe by p-G2BDS is explored under various conditions and X-ray diffraction provides a measurement of the high-pressure, room temperature Xe and CO2 sorption isotherms. Though p-G2BDS is formally metastable relative to the “collapsed”, nonporous polymorph, np-G2BDS, a sample of p-G2BDS survived for almost two decades under ambient conditions. np-G2BDS reverts to zCO2@p-G2BDS or yXe@p-G2BDS (y,z=variable) when pressure of CO2 or Xe, respectively, is applied.
KW - gas sorption
KW - guanidinium sulfonates
KW - hydrogen-bonded organic frameworks
KW - porosity
KW - porous molecular solids
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U2 - 10.1002/anie.201911861
DO - 10.1002/anie.201911861
M3 - Article
C2 - 31663253
AN - SCOPUS:85076214123
SN - 1433-7851
VL - 59
SP - 1997
EP - 2002
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 5
ER -