Snapshots of a solid-state transformation

coexistence of three phases trapped in one crystal

G. Aromí, C. M. Beavers, J. Sánchez Costa, G. A. Craig, G. Mínguez Espallargas, A. Orera, O. Roubeau

Research output: Contribution to journalArticle

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Abstract

Crystal-to-crystal transformations have been crucial in the understanding of solid-state processes, since these may be studied in detail by means of single crystal X-ray diffraction (SCXRD) techniques. The description of the mechanisms and potential intermediates of those processes remains very challenging. In fact, solid-state transient states have rarely been observed, at least to a sufficient level of detail. We have investigated the process of guest extrusion from the non-porous molecular material [Fe(bpp)(H2L)](ClO4)2·1.5C3H6O (bpp = 2,6-bis(pyrazol-3-yl)pyridine; H2L = 2,6-bis(5-(2-methoxyphenyl)-pyrazol-3-yl)pyridine; C3H6O = acetone), which occurs through ordered diffusion of acetone in a crystal-to-crystal manner, leading to dramatic structural changes. The slow kinetics of the transition allows thermal trapping of the system at various intermediate stages. The transiting single crystal can be then examined at these points through synchrotron SCXRD, offering a window upon the mechanism of the transformation at the molecular scale. These experiments have unveiled the development of an ordered intermediate phase, distinct from the initial and the final states, coexisting as the process advances with either of these two phases or, at a certain moment with both of them. The new intermediate phase has been structurally characterized in full detail by SCXRD, providing insights into the mechanism of this diffusion triggered solid-state phenomenon. The process has been also followed by calorimetry, optical microscopy, local Raman spectroscopy and powder X-ray diffraction. The discovery and description of an intermediate ordered state in a molecular solid-state transformation is of great interest and will help to understand the mechanistic details and reaction pathways underlying these transformations.
Original languageEnglish
Pages (from-to)2907-2915
Number of pages9
JournalChemical Science
Volume7
Issue number4
DOIs
Publication statusPublished - 5 Jan 2016

Fingerprint

Single crystals
Crystals
Acetone
X ray diffraction
Diffusion in solids
Calorimetry
Synchrotrons
X ray powder diffraction
Optical microscopy
Extrusion
Raman spectroscopy
Kinetics
Experiments
Hot Temperature
perchlorate
pyridine
2,6-bis(pyrazol-3-yl)pyridine

Keywords

  • solid-state transformation
  • crystal-to-crystal transformations
  • X-ray diffraction

Cite this

Aromí, G., Beavers, C. M., Sánchez Costa, J., Craig, G. A., Mínguez Espallargas, G., Orera, A., & Roubeau, O. (2016). Snapshots of a solid-state transformation: coexistence of three phases trapped in one crystal. Chemical Science, 7(4), 2907-2915. https://doi.org/10.1039/C5SC04287A
Aromí, G. ; Beavers, C. M. ; Sánchez Costa, J. ; Craig, G. A. ; Mínguez Espallargas, G. ; Orera, A. ; Roubeau, O. / Snapshots of a solid-state transformation : coexistence of three phases trapped in one crystal. In: Chemical Science. 2016 ; Vol. 7, No. 4. pp. 2907-2915.
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Aromí, G, Beavers, CM, Sánchez Costa, J, Craig, GA, Mínguez Espallargas, G, Orera, A & Roubeau, O 2016, 'Snapshots of a solid-state transformation: coexistence of three phases trapped in one crystal', Chemical Science, vol. 7, no. 4, pp. 2907-2915. https://doi.org/10.1039/C5SC04287A

Snapshots of a solid-state transformation : coexistence of three phases trapped in one crystal. / Aromí, G.; Beavers, C. M.; Sánchez Costa, J.; Craig, G. A.; Mínguez Espallargas, G.; Orera, A.; Roubeau, O.

In: Chemical Science, Vol. 7, No. 4, 05.01.2016, p. 2907-2915.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Snapshots of a solid-state transformation

T2 - coexistence of three phases trapped in one crystal

AU - Aromí, G.

AU - Beavers, C. M.

AU - Sánchez Costa, J.

AU - Craig, G. A.

AU - Mínguez Espallargas, G.

AU - Orera, A.

AU - Roubeau, O.

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N2 - Crystal-to-crystal transformations have been crucial in the understanding of solid-state processes, since these may be studied in detail by means of single crystal X-ray diffraction (SCXRD) techniques. The description of the mechanisms and potential intermediates of those processes remains very challenging. In fact, solid-state transient states have rarely been observed, at least to a sufficient level of detail. We have investigated the process of guest extrusion from the non-porous molecular material [Fe(bpp)(H2L)](ClO4)2·1.5C3H6O (bpp = 2,6-bis(pyrazol-3-yl)pyridine; H2L = 2,6-bis(5-(2-methoxyphenyl)-pyrazol-3-yl)pyridine; C3H6O = acetone), which occurs through ordered diffusion of acetone in a crystal-to-crystal manner, leading to dramatic structural changes. The slow kinetics of the transition allows thermal trapping of the system at various intermediate stages. The transiting single crystal can be then examined at these points through synchrotron SCXRD, offering a window upon the mechanism of the transformation at the molecular scale. These experiments have unveiled the development of an ordered intermediate phase, distinct from the initial and the final states, coexisting as the process advances with either of these two phases or, at a certain moment with both of them. The new intermediate phase has been structurally characterized in full detail by SCXRD, providing insights into the mechanism of this diffusion triggered solid-state phenomenon. The process has been also followed by calorimetry, optical microscopy, local Raman spectroscopy and powder X-ray diffraction. The discovery and description of an intermediate ordered state in a molecular solid-state transformation is of great interest and will help to understand the mechanistic details and reaction pathways underlying these transformations.

AB - Crystal-to-crystal transformations have been crucial in the understanding of solid-state processes, since these may be studied in detail by means of single crystal X-ray diffraction (SCXRD) techniques. The description of the mechanisms and potential intermediates of those processes remains very challenging. In fact, solid-state transient states have rarely been observed, at least to a sufficient level of detail. We have investigated the process of guest extrusion from the non-porous molecular material [Fe(bpp)(H2L)](ClO4)2·1.5C3H6O (bpp = 2,6-bis(pyrazol-3-yl)pyridine; H2L = 2,6-bis(5-(2-methoxyphenyl)-pyrazol-3-yl)pyridine; C3H6O = acetone), which occurs through ordered diffusion of acetone in a crystal-to-crystal manner, leading to dramatic structural changes. The slow kinetics of the transition allows thermal trapping of the system at various intermediate stages. The transiting single crystal can be then examined at these points through synchrotron SCXRD, offering a window upon the mechanism of the transformation at the molecular scale. These experiments have unveiled the development of an ordered intermediate phase, distinct from the initial and the final states, coexisting as the process advances with either of these two phases or, at a certain moment with both of them. The new intermediate phase has been structurally characterized in full detail by SCXRD, providing insights into the mechanism of this diffusion triggered solid-state phenomenon. The process has been also followed by calorimetry, optical microscopy, local Raman spectroscopy and powder X-ray diffraction. The discovery and description of an intermediate ordered state in a molecular solid-state transformation is of great interest and will help to understand the mechanistic details and reaction pathways underlying these transformations.

KW - solid-state transformation

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KW - X-ray diffraction

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DO - 10.1039/C5SC04287A

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SN - 2041-6520

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Aromí G, Beavers CM, Sánchez Costa J, Craig GA, Mínguez Espallargas G, Orera A et al. Snapshots of a solid-state transformation: coexistence of three phases trapped in one crystal. Chemical Science. 2016 Jan 5;7(4):2907-2915. https://doi.org/10.1039/C5SC04287A