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Joint Experimental and Computational Investigation of the Flexibility of a Diacetylene-Based Mixed-Linker MOF: Revealing the Existence of Two Low-Temperature Phase Transitions and the Presence of Colossal Positive and Giant Negative Thermal Expansions.
Journal article

Joint Experimental and Computational Investigation of the Flexibility of a Diacetylene-Based Mixed-Linker MOF: Revealing the Existence of Two Low-Temperature Phase Transitions and the Presence of Colossal Positive and Giant Negative Thermal Expansions.

  • Duarte Rodrigues A Institut Charles Gerhardt, UMR 5253 CNRS-ENSCM-UM, Equipe CMOS, Université de Montpellier, Bât. 17, CC 1701, Place Eugène Bataillon, 34095, Montpellier Cedex 5, France.
  • Fahsi K Institut Charles Gerhardt, UMR 5253 CNRS-ENSCM-UM, Equipe CMOS, Université de Montpellier, Bât. 17, CC 1701, Place Eugène Bataillon, 34095, Montpellier Cedex 5, France.
  • Dumail X Institut Charles Gerhardt, UMR 5253 CNRS-ENSCM-UM, Equipe CMOS, Université de Montpellier, Bât. 17, CC 1701, Place Eugène Bataillon, 34095, Montpellier Cedex 5, France.
  • Masquelez N Institut Européen des Membranes, UMR 5635 CNRS-ENSCM-UM, Université de Montpellier, Case Courrier 047, Place Eugène Bataillon, 34095, Montpellier Cedex 5, France.
  • van der Lee A Institut Européen des Membranes, UMR 5635 CNRS-ENSCM-UM, Université de Montpellier, Case Courrier 047, Place Eugène Bataillon, 34095, Montpellier Cedex 5, France.
  • Mallet-Ladeira S Institut de Chimie de Toulouse (FR 2599), Université Paul Sabatier, 118 route de Narbonne, 31062, Toulouse Cedex 9, France.
  • Sibille R Laboratory for Neutron Scattering and Imaging, Paul Scherrer Institut, 5232, Villigen PSI, Switzerland.
  • Filhol JS Institut Charles Gerhardt, UMR 5253 CNRS-ENSCM-UM, Equipe CTMM, Université de Montpellier, Bât. 15, CC 1501, Place Eugène Bataillon, 34095, Montpellier Cedex 5, France.
  • Dutremez SG Institut Charles Gerhardt, UMR 5253 CNRS-ENSCM-UM, Equipe CMOS, Université de Montpellier, Bât. 17, CC 1701, Place Eugène Bataillon, 34095, Montpellier Cedex 5, France.
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  • 2017-11-09
Published in:
  • Chemistry (Weinheim an der Bergstrasse, Germany). - 2018
DFT calculations
coordination polymer
crystal structure
diacetylene
phase transition
polymorphism
English Solvothermal reaction in N,N-dimethylformamide (DMF) between 1,6-bis(1-imidazolyl)-2,4-hexadiyne monohydrate (L1⋅H2 O), isophthalic acid (H2 L2), and Zn(NO3 )2 ⋅6 H2 O gives the diacetylene-based mixed-ligand coordination polymer {[Zn(L1)(L2)](DMF)2 }n (UMON-44) in 38 % yield. Combination of DSC with variable-temperature single-crystal X-ray diffraction revealed the occurrence of two phase transitions spanning the ranges 129-144 K and 158-188 K. Furthermore, the three structurally similar phases of UMON-44 show giant negative and/or colossal positive thermal expansions. These unusual phenomena exist without any change in the contents of the unit cell. DFT calculations using the PBE+D3 dispersion scheme were able to distinguish between these polymorphs by accurately reproducing their salient structural features, although corrections in the size of the unit cell turned out to be necessary for the high-temperature phase to account for its large thermal expansion. In addition, the infrared spectra (vibration frequencies and peak intensities) of these theoretical models were calculated, allowing for univocal identification of the corresponding polymorphs. Last, the limits of our computational method were tested by calculating the phase transition temperatures and their associated enthalpies, and the derived figures compare favorably with the values determined experimentally.
Language
  • English
Open access status
closed
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Persistent URL
https://sonar.ch/global/documents/93014
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