Snapshots of a solid-state transformation: coexistence of three phases trapped in one crystal
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 diffusionmore »
- Authors:
-
- Univ. de Barcelona, Barcelona (Spain). Dept. de Quimica Inorganica
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
- Univ. de Valencia, Paterna, Valencia (Spain). Inst. de Ciencia Molecular (ICMol)
- Univ. de Zaragoza, Zaragoza (Spain). Inst. de Ciencia de Materiales de Aragon (ICMA)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1415953
- Grant/Contract Number:
- AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemical Science
- Additional Journal Information:
- Journal Volume: 7; Journal Issue: 4; Journal ID: ISSN 2041-6520
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Aromí, G., Beavers, C. M., Sánchez Costa, J., Craig, G. A., Mínguez Espallargas, G., Orera, A., and Roubeau, O. Snapshots of a solid-state transformation: coexistence of three phases trapped in one crystal. United States: N. p., 2016.
Web. doi: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. United States. https://doi.org/10.1039/C5SC04287A
Aromí, G., Beavers, C. M., Sánchez Costa, J., Craig, G. A., Mínguez Espallargas, G., Orera, A., and Roubeau, O. Tue .
"Snapshots of a solid-state transformation: coexistence of three phases trapped in one crystal". United States. https://doi.org/10.1039/C5SC04287A. https://www.osti.gov/servlets/purl/1415953.
@article{osti_1415953,
title = {Snapshots of a solid-state transformation: coexistence of three phases trapped in one crystal},
author = {Aromí, G. and Beavers, C. M. and Sánchez Costa, J. and Craig, G. A. and Mínguez Espallargas, G. and Orera, A. and Roubeau, O.},
abstractNote = {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. Lastly, 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.},
doi = {10.1039/C5SC04287A},
journal = {Chemical Science},
number = 4,
volume = 7,
place = {United States},
year = {Tue Jan 05 00:00:00 EST 2016},
month = {Tue Jan 05 00:00:00 EST 2016}
}
Web of Science
Figures / Tables:
Works referenced in this record:
On the hydrates of codeine phosphate: the remarkable influence of hydrogen bonding on the crystal size
journal, January 2014
- Runčevski, Tomče; Petruševski, Gjorgji; Makreski, Petre
- Chem. Commun., Vol. 50, Issue 53
The Thermodynamic Properties of Acetone
journal, January 1957
- Pennington, Robert E.; Kobe, Kenneth A.
- Journal of the American Chemical Society, Vol. 79, Issue 2
Molecular motor-driven abrupt anisotropic shape change in a single crystal of a Ni complex
journal, October 2014
- Yao, Zi-Shuo; Mito, Masaki; Kamachi, Takashi
- Nature Chemistry, Vol. 6, Issue 12
Colossal positive and negative thermal expansion and thermosalient effect in a pentamorphic organometallic martensite
journal, September 2014
- Panda, Manas K.; Runčevski, Tomče; Chandra Sahoo, Subash
- Nature Communications, Vol. 5, Issue 1
Gas Adsorption Sites in a Large-Pore Metal-Organic Framework
journal, August 2005
- Rowsell, Jesse L. C.; Spencer, Elinor C.; Eckert, Juergen
- Science, Vol. 309, Issue 5739, p. 1350-1354
Structural Reevaluation of the Electrophilic Hypervalent Iodine Reagent for Trifluoromethylthiolation Supported by the Crystalline Sponge Method for X-ray Analysis
journal, February 2014
- Vinogradova, Ekaterina V.; Müller, Peter; Buchwald, Stephen L.
- Angewandte Chemie International Edition, Vol. 53, Issue 12
Beyond post-synthesis modification: evolution of metal–organic frameworks via building block replacement
journal, January 2014
- Deria, Pravas; Mondloch, Joseph E.; Karagiaridi, Olga
- Chem. Soc. Rev., Vol. 43, Issue 16
Preparation and guest-uptake protocol for a porous complex useful for 'crystal-free' crystallography
journal, January 2014
- Inokuma, Yasuhide; Yoshioka, Shota; Ariyoshi, Junko
- Nature Protocols, Vol. 9, Issue 2
Topotactic reactions in inorganic oxy-compounds
journal, January 1962
- Glasser, L. S. Dent; Glasser, F. P.; Taylor, H. F. W.
- Quarterly Reviews, Chemical Society, Vol. 16, Issue 4
Direct Crystallographic Observation of a Coordinatively Unsaturated Transition-Metal Complex in situ Generated within a Self-Assembled Cage
journal, May 2006
- Kawano, Masaki; Kobayashi, Yasuhiro; Ozeki, Tomoji
- Journal of the American Chemical Society, Vol. 128, Issue 20
Coupled Crystallographic Order–Disorder and Spin State in a Bistable Molecule: Multiple Transition Dynamics
journal, February 2011
- Craig, Gavin A.; Sánchez Costa, José; Roubeau, Olivier
- Chemistry – A European Journal, Vol. 17, Issue 11
Direct visualization of a guest-triggered crystal deformation based on a flexible ultramicroporous framework
journal, September 2013
- Zhou, Hao-Long; Lin, Rui-Biao; He, Chun-Ting
- Nature Communications, Vol. 4, Issue 1
Organoplatinum crystals for gas-triggered switches
journal, August 2000
- Albrecht, Martin; Lutz, Martin; Spek, Anthony L.
- Nature, Vol. 406, Issue 6799
Concerted Spin Crossover and Symmetry Breaking Yield Three Thermally and One Light-Induced Crystallographic Phases of a Molecular Material
journal, November 2009
- Bréfuelâ , Nicolas; Watanabe, Hiroshi; Toupet, Loic
- Angewandte Chemie International Edition, Vol. 48, Issue 49
Reversible Surface Morphology Changes of a Photochromic Diarylethene Single Crystal by Photoirradiation
journal, March 2001
- Irie, M.
- Science, Vol. 291, Issue 5509
Chemical Modification of a Bridging Ligand Inside a Metal–Organic Framework while Maintaining the 3D Structure
journal, April 2008
- Costa, José Sánchez; Gamez, Patrick; Black, Cory A.
- European Journal of Inorganic Chemistry, Vol. 2008, Issue 10, p. 1551-1554
Symmetry-breaking structural phase transitions in spin crossover complexes
journal, April 2015
- Shatruk, Michael; Phan, Hoa; Chrisostomo, Bruno A.
- Coordination Chemistry Reviews, Vol. 289-290
Guest Transport in a Nonporous Organic Solid via Dynamic van der Waals Cooperativity
journal, November 2002
- Atwood, J. L.; Barbour, L. J.; Jerga, A.
- Science, Vol. 298, Issue 5595
Metal–Macrocycle Framework (MMF): Supramolecular Nano-Channel Surfaces with Shape Sorting Capability
journal, January 2012
- Tashiro, Shohei; Kubota, Ryou; Shionoya, Mitsuhiko
- Journal of the American Chemical Society, Vol. 134, Issue 5
Single-crystal X-ray diffraction studies on structural transformations of porous coordination polymers
journal, January 2014
- Zhang, Jie-Peng; Liao, Pei-Qin; Zhou, Hao-Long
- Chem. Soc. Rev., Vol. 43, Issue 16
Thermal, pressure and light switchable spin-crossover materials
journal, January 2005
- Real, José Antonio; Gaspar, Ana Belén; Muñoz, M. Carmen
- Dalton Transactions, Issue 12
Trapping of a Spatial Transient State During the Framework Transformation of a Porous Coordination Polymer
journal, March 2014
- Kondo, Mio; Furukawa, Shuhei; Hirai, Kenji
- Journal of the American Chemical Society, Vol. 136, Issue 13
Capturing snapshots of post-synthetic metallation chemistry in metal–organic frameworks
journal, September 2014
- Bloch, Witold M.; Burgun, Alexandre; Coghlan, Campbell J.
- Nature Chemistry, Vol. 6, Issue 10
Diffraction Studies of Photoexcited Crystals: Metastable Nitrosyl-Linkage Isomers of Sodium Nitroprusside
journal, March 1997
- Carducci, M. D.; Pressprich, M. R.; Coppens, P.
- Journal of the American Chemical Society, Vol. 119, Issue 11
Iron Spin-Crossover compounds: from fundamental studies to practical applications
journal, January 2009
- Gamez, Patrick; Costa, José Sánchez; Quesada, Manuel
- Dalton Transactions, Issue 38
Guest-Dependent Spin Crossover in a Nanoporous Molecular Framework Material
journal, November 2002
- Halder, G. J.
- Science, Vol. 298, Issue 5599
Experimental Establishment of Mother–Daughter Orientation Relationships and Twinning Effects in Phase Transitions: A Great Legacy from Jack Gougoutas and Peggy Etter
journal, June 2015
- Posner, Shai R.; Lorson, Logan C.; Gell, Aaron R.
- Crystal Growth & Design, Vol. 15, Issue 7
A flexible interpenetrating coordination framework with a bimodal porous functionality
journal, January 2007
- Maji, Tapas Kumar; Matsuda, Ryotaro; Kitagawa, Susumu
- Nature Materials, Vol. 6, Issue 2
X-ray analysis on the nanogram to microgram scale using porous complexes
journal, March 2013
- Inokuma, Yasuhide; Yoshioka, Shota; Ariyoshi, Junko
- Nature, Vol. 495, Issue 7442
Reversible Topochemical Transformation of a Soft Crystal of a Coordination Polymer
journal, October 2007
- Ghosh, Sujit K.; Zhang, Jie-Peng; Kitagawa, Susumu
- Angewandte Chemie International Edition, Vol. 46, Issue 42
A Springlike 3D-Coordination Network That Shrinks or Swells in a Crystal-to-Crystal Manner upon Guest Removal or Readsorption
journal, September 2002
- Biradha, Kumar; Fujita, Makoto
- Angewandte Chemie International Edition, Vol. 41, Issue 18
A Bistable Porous Coordination Polymer with a Bond-Switching Mechanism Showing Reversible Structural and Functional Transformations
journal, November 2008
- Ghosh, Sujit K.; Kaneko, Wakako; Kiriya, Daisuke
- Angewandte Chemie International Edition, Vol. 47, Issue 46
Mechanical gas capture and release in a network solid via multiple single-crystalline transformations
journal, January 2008
- Chandler, Brett D.; Enright, Gary D.; Udachin, Konstantin A.
- Nature Materials, Vol. 7, Issue 3
Direct Observation and Quantification of CO 2 Binding Within an Amine-Functionalized Nanoporous Solid
journal, October 2010
- Vaidhyanathan, Ramanathan; Iremonger, Simon S.; Shimizu, George K. H.
- Science, Vol. 330, Issue 6004
X-ray observation of a transient hemiaminal trapped in a porous network
journal, October 2009
- Kawamichi, Takehide; Haneda, Tsuyoshi; Kawano, Masaki
- Nature, Vol. 461, Issue 7264
Molecular Crystals on the Move: From Single-Crystal-to-Single-Crystal Photoreactions to Molecular Machinery
journal, December 2007
- Garcia-Garibay, Miguel A.
- Angewandte Chemie International Edition, Vol. 46, Issue 47
Three-Way Crystal-to-Crystal Reversible Transformation and Controlled Spin Switching by a Nonporous Molecular Material
journal, February 2014
- Costa, José Sánchez; Rodríguez-Jiménez, Santiago; Craig, Gavin A.
- Journal of the American Chemical Society, Vol. 136, Issue 10
Structural phase transition in the spin-crossover complex studied by x-ray diffraction
journal, October 2010
- Lakhloufi, S.; Guionneau, P.; Lemée-Cailleau, M. H.
- Physical Review B, Vol. 82, Issue 13
Tuning the magneto-structural properties of non-porous coordination polymers by HCl chemisorption
journal, January 2012
- Coronado, Eugenio; Giménez-Marqués, Mónica; Espallargas, Guillermo Mínguez
- Nature Communications, Vol. 3, Issue 1
Crystalline molecular flasks
journal, April 2011
- Inokuma, Yasuhide; Kawano, Masaki; Fujita, Makoto
- Nature Chemistry, Vol. 3, Issue 5
Reversible Topochemical Transformation of a Soft Crystal of a Coordination Polymer
journal, October 2007
- Ghosh, Sujit K.; Zhang, Jie-Peng; Kitagawa, Susumu
- Angewandte Chemie, Vol. 119, Issue 42
A Bistable Porous Coordination Polymer with a Bond-Switching Mechanism Showing Reversible Structural and Functional Transformations
journal, November 2008
- Ghosh, Sujit K.; Kaneko, Wakako; Kiriya, Daisuke
- Angewandte Chemie, Vol. 120, Issue 46
Structural Reevaluation of the Electrophilic Hypervalent Iodine Reagent for Trifluoromethylthiolation Supported by the Crystalline Sponge Method for X-ray Analysis
journal, February 2014
- Vinogradova, Ekaterina V.; Müller, Peter; Buchwald, Stephen L.
- Angewandte Chemie, Vol. 126, Issue 12
Concerted Spin Crossover and Symmetry Breaking Yield Three Thermally and One Light-Induced Crystallographic Phases of a Molecular Material
journal, November 2009
- Bréfuelâ , Nicolas; Watanabe, Hiroshi; Toupet, Loic
- Angewandte Chemie, Vol. 121, Issue 49
Works referencing / citing this record:
Non-Porous Iron(II)-Based Sensor: Crystallographic Insights into a Cycle of Colorful Guest-Induced Topotactic Transformations
journal, October 2016
- Rodríguez-Jiménez, Santiago; Feltham, Humphrey L. C.; Brooker, Sally
- Angewandte Chemie, Vol. 128, Issue 48
Guest-, Light- and Thermally-Modulated Spin Crossover in [Fe II 2 ] Supramolecular Helicates
journal, May 2016
- Darawsheh, Mohanad; Barrios, Leoni A.; Roubeau, Olivier
- Chemistry - A European Journal, Vol. 22, Issue 25
Water-Mediated Structural Transformations of Cu II 5-Halonicotinates Coordination Networks with Distinct Mechanisms
journal, July 2017
- Li, Cheng-Peng; Zhou, Hang; Ju, Yue
- Chemistry - A European Journal, Vol. 23, Issue 53
Two Consecutive Magneto-Structural Gas-Solid Transformations in Non-Porous Molecular Materials
journal, July 2018
- Miguel-Donet, Julia; López-Cabrelles, Javier; Calvo Galve, Néstor
- Chemistry - A European Journal, Vol. 24, Issue 47
Spin crossover properties of enantiomers, co-enantiomers, racemates, and co-racemates
journal, January 2016
- Qin, Long-Fang; Pang, Chun-Yan; Han, Wang-Kang
- Dalton Transactions, Vol. 45, Issue 17
Spin crossover Fe( ii ) complexes of a cross-bridged cyclam derivative
journal, January 2018
- Drahoš, Bohuslav; Trávníček, Zdeněk
- Dalton Transactions, Vol. 47, Issue 17
Unravelling the spin-state of solvated [Fe(bpp) 2 ] 2+ spin-crossover complexes: structure–function relationship
journal, January 2018
- Giménez-López, Maria del Carmen; Clemente-León, Miguel; Giménez-Saiz, Carlos
- Dalton Transactions, Vol. 47, Issue 31
Solution-mediated and single-crystal to single-crystal transformations of cucurbit[6]uril host–guest complexes with dopamine
journal, January 2020
- Danylyuk, Oksana; Worzakowska, Marta; Osypiuk-Tomasik, Joanna
- CrystEngComm, Vol. 22, Issue 4
Single-crystal-to-single-crystal transformations triggered by dehydration in polyoxometalate-based compounds
journal, October 2018
- Reinoso, Santiago; Artetxe, Beñat; Gutiérrez-Zorrilla, Juan M.
- Acta Crystallographica Section C Structural Chemistry, Vol. 74, Issue 11
Non-Porous Iron(II)-Based Sensor: Crystallographic Insights into a Cycle of Colorful Guest-Induced Topotactic Transformations
journal, October 2016
- Rodríguez-Jiménez, Santiago; Feltham, Humphrey L. C.; Brooker, Sally
- Angewandte Chemie International Edition, Vol. 55, Issue 48
Figures / Tables found in this record: