Anisotropic Thermal and Guest-Induced Responses of an Ultramicroporous Framework with Rigid Linkers

Josie Auckett, Samuel G Duyker, Ekaterina Izgorodina, Chris S Hawes, David R Turner, Stuart R Batten, Vanessa Peterson

Research output: Contribution to journalArticleResearchpeer-review

Abstract

The interdependent effects of temperature and guest uptake on the structure of the ultramicroporous metal–organic framework [Cu3(cdm)4] (cdm=C(CN)2(CONH2)) were explored in detail by using in situ neutron scattering and density functional theory calculations. The tetragonal lattice displays an anisotropic thermal response related to a hinged “lattice-fence” mechanism, unusual for this topology, which is facilitated by pivoting of the rigid cdm anion about the Cu nodes. Calculated pore-size metrics clearly illustrate the potential for temperature-mediated adsorption in ultramicroporous frameworks due to thermal fluctuations of the pore diameter near the value of the target guest kinetic diameter, though in [Cu3(cdm)4] this is counteracted by a competing contraction of the pore with increasing temperature as a result of the anisotropic lattice response.

Original languageEnglish
Pages (from-to)4774-4779
Number of pages6
JournalChemistry - A European Journal
Volume24
Issue number19
DOIs
Publication statusPublished - 3 Apr 2018

Keywords

  • density functional calculations
  • gas sorption
  • metal–organic frameworks
  • negative thermal expansion
  • neutron diffraction

Cite this

@article{0e3fc5523f674290ac40e2b2281ed172,
title = "Anisotropic Thermal and Guest-Induced Responses of an Ultramicroporous Framework with Rigid Linkers",
abstract = "The interdependent effects of temperature and guest uptake on the structure of the ultramicroporous metal–organic framework [Cu3(cdm)4] (cdm=C(CN)2(CONH2)−) were explored in detail by using in situ neutron scattering and density functional theory calculations. The tetragonal lattice displays an anisotropic thermal response related to a hinged “lattice-fence” mechanism, unusual for this topology, which is facilitated by pivoting of the rigid cdm anion about the Cu nodes. Calculated pore-size metrics clearly illustrate the potential for temperature-mediated adsorption in ultramicroporous frameworks due to thermal fluctuations of the pore diameter near the value of the target guest kinetic diameter, though in [Cu3(cdm)4] this is counteracted by a competing contraction of the pore with increasing temperature as a result of the anisotropic lattice response.",
keywords = "density functional calculations, gas sorption, metal–organic frameworks, negative thermal expansion, neutron diffraction",
author = "Josie Auckett and Duyker, {Samuel G} and Ekaterina Izgorodina and Hawes, {Chris S} and Turner, {David R} and Batten, {Stuart R} and Vanessa Peterson",
year = "2018",
month = "4",
day = "3",
doi = "10.1002/chem.201800261",
language = "English",
volume = "24",
pages = "4774--4779",
journal = "Chemistry - A European Journal",
issn = "1521-3765",
publisher = "Wiley-VCH Verlag GmbH & Co. KGaA",
number = "19",

}

Anisotropic Thermal and Guest-Induced Responses of an Ultramicroporous Framework with Rigid Linkers. / Auckett, Josie; Duyker, Samuel G; Izgorodina, Ekaterina; Hawes, Chris S; Turner, David R; Batten, Stuart R; Peterson, Vanessa.

In: Chemistry - A European Journal, Vol. 24, No. 19, 03.04.2018, p. 4774-4779.

Research output: Contribution to journalArticleResearchpeer-review

TY - JOUR

T1 - Anisotropic Thermal and Guest-Induced Responses of an Ultramicroporous Framework with Rigid Linkers

AU - Auckett, Josie

AU - Duyker, Samuel G

AU - Izgorodina, Ekaterina

AU - Hawes, Chris S

AU - Turner, David R

AU - Batten, Stuart R

AU - Peterson, Vanessa

PY - 2018/4/3

Y1 - 2018/4/3

N2 - The interdependent effects of temperature and guest uptake on the structure of the ultramicroporous metal–organic framework [Cu3(cdm)4] (cdm=C(CN)2(CONH2)−) were explored in detail by using in situ neutron scattering and density functional theory calculations. The tetragonal lattice displays an anisotropic thermal response related to a hinged “lattice-fence” mechanism, unusual for this topology, which is facilitated by pivoting of the rigid cdm anion about the Cu nodes. Calculated pore-size metrics clearly illustrate the potential for temperature-mediated adsorption in ultramicroporous frameworks due to thermal fluctuations of the pore diameter near the value of the target guest kinetic diameter, though in [Cu3(cdm)4] this is counteracted by a competing contraction of the pore with increasing temperature as a result of the anisotropic lattice response.

AB - The interdependent effects of temperature and guest uptake on the structure of the ultramicroporous metal–organic framework [Cu3(cdm)4] (cdm=C(CN)2(CONH2)−) were explored in detail by using in situ neutron scattering and density functional theory calculations. The tetragonal lattice displays an anisotropic thermal response related to a hinged “lattice-fence” mechanism, unusual for this topology, which is facilitated by pivoting of the rigid cdm anion about the Cu nodes. Calculated pore-size metrics clearly illustrate the potential for temperature-mediated adsorption in ultramicroporous frameworks due to thermal fluctuations of the pore diameter near the value of the target guest kinetic diameter, though in [Cu3(cdm)4] this is counteracted by a competing contraction of the pore with increasing temperature as a result of the anisotropic lattice response.

KW - density functional calculations

KW - gas sorption

KW - metal–organic frameworks

KW - negative thermal expansion

KW - neutron diffraction

UR - http://www.scopus.com/inward/record.url?scp=85043356633&partnerID=8YFLogxK

U2 - 10.1002/chem.201800261

DO - 10.1002/chem.201800261

M3 - Article

VL - 24

SP - 4774

EP - 4779

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 1521-3765

IS - 19

ER -