Inflatable porous organic crystals
Source abstract
Abstract
Abstract The relationship between changes in the macroscopic dimensions of a solid and its environmental conditions such as temperature or pressure can be rationalized at the molecular level. The controllable conversion of such external stimuli to mechanical energy can be exploited to construct mechanical or electromechanical devices, which are sometimes required to operate in extreme environments. Here we describe predominantly unidirectional expansion and contraction of an acicular porous molecular crystal owing to gas uptake or release. Using complementary in situ structural and photomicrographic techniques, we have obtained molecular-level insights that correlate macroscopic linear expansion of the crystal by up to 10% with the application of gas-specific pressure. We also demonstrate that the expansion of the needle axis with pressure can be modelled using the well-known Langmuir–Freundlich equation, thereby providing a convenient means of relating pressure and guest-induced linear expansion within a bounded continuum.
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Research context
OpenAlex topics: Supramolecular Chemistry and Complexes · Luminescence and Fluorescent Materials · Supramolecular Self-Assembly in Materials
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (46)
Show source-provided references
1. Sargent, R. Evaluating dimensional stability in solid wood: a review of current practice. J. Wood Sci. 65, 36 (2019).10.1186/s10086-019-1817-1 ↗
2. Yong, R. N. Soil suction and soil-water potentials in swelling clays in engineered clay barriers. Eng. Geol. 54, 3–13 (1999).10.1016/S0013-7952(99)00056-3 ↗
3. Feng, W. & Wang, Z. Tailoring the swelling-shrinkable behavior of hydrogels for biomedical applications. Adv. Sci. 10, e2303326 (2023).10.1002/advs.202303326 ↗
4. Vandamme, M., Brochard, L., Lecampion, B. & Coussy, O. Adsorption and strain: the CO2-induced swelling of coal. J. Mech. Phys. Solids 58, 1489–1505 (2010).10.1016/j.jmps.2010.07.014 ↗
5. Desiraju, G. R. Crystal: In search of clarity. Nature 423, 485 (2003).10.1038/423485a ↗
6. Naumov, P. et al. The rise of the dynamic crystals. J. Am. Chem. Soc. 142, 13256–13272 (2020).10.1021/jacs.0c05440 ↗
7. Ahmed, E., Karothu, D. P. & Naumov, P. Crystal adaptronics: mechanically reconfigurable elastic and superelastic molecular crystals. Angew. Chem. Int. Ed. 57, 8837–8846 (2018).10.1002/anie.201800137 ↗
8. Yaghi, O. M. et al. Reticular synthesis and the design of new materials. Nature 423, 705–714 (2003).10.1038/nature01650 ↗
9. Geng, K. et al. Covalent organic frameworks: design, synthesis, and functions. Chem. Rev. 120, 8814–8933 (2020).10.1021/acs.chemrev.9b00550 ↗
10. Barbour, L. J. Crystal porosity and the burden of proof. Chem. Commun. 1163–1168 (2006).10.1039/b515612m ↗
11. Eaby, A. C. et al. Dehydration of a crystal hydrate at subglacial temperatures. Nature 616, 288–292 (2023).10.1038/s41586-023-05749-7 ↗
12. Bojdys, M. J. et al. Supramolecular engineering of intrinsic and extrinsic porosity in covalent organic cages. J. Am. Chem. Soc. 133, 16566–16571 (2011).10.1021/ja2056374 ↗
13. Connolly, M. L. Analytical molecular surface calculation. J. Appl. Crystallogr. 16, 548–558 (1983).10.1107/S0021889883010985 ↗
14. Connolly, M. L. Computation of molecular volume. J. Am. Chem. Soc. 107, 1118–1124 (1985).10.1021/ja00291a006 ↗
15. Van Heerden, D. P. & Barbour, L. J. Guest-occupiable space in the crystalline solid state: a simple rule-of-thumb for predicting occupancy. Chem. Soc. Rev. 50, 735–749 (2021).10.1039/D0CS01040E ↗
16. Eaby, A. C. et al. Programmed pore-shape fixing in a soft porous molecular crystal—navigating the phase interconversion landscape. Angew. Chem. Int. Ed. 62, e202304152 (2023).10.1002/anie.202304152 ↗
17. MacRae, C. F. et al. Mercury 4.0: from visualization to analysis, design and prediction. J. Appl. Crystallogr. 53, 226–235 (2020).10.1107/S1600576719014092 ↗
18. Sing, K. S. W. et al. Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity (recommendations 1984). Pure Appl. Chem. 57, 603–619 (1985).10.1351/pac198557040603 ↗
19. Horike, S., Shimomura, S. & Kitagawa, S. Soft porous crystals. Nat. Chem. 1, 695–704 (2009).10.1038/nchem.444 ↗
20. Dong, Q. et al. Tuning gate-opening of a flexible metal–organic framework for ternary gas sieving separation. Angew. Chem. Int. Ed. 59, 22756–22762 (2020).10.1002/anie.202011802 ↗
21. Sips, R. On the structure of a catalyst surface. J. Chem. Phys. 16, 490–495 (1948).10.1063/1.1746922 ↗
22. Jacobs, T. et al. In situ X-ray structural studies of a flexible host responding to incremental gas loading. Angew. Chem. Int. Ed. 51, 4913–4916 (2012).10.1002/anie.201201281 ↗
23. Biradha, K. & Fujita, M. A springlike 3D-coordination network that shrinks or swells in a crystal-to-crystal manner upon guest removal or readsorption. Angew. Chem. Int. Ed. 41, 3392–3395 (2002).10.1002/1521-3773(20020916)41:18<3392::AID-ANIE3392>3.0.CO;2-V ↗
24. Takamizawa, S. et al. Crystal transformation and host molecular motions in CO2 adsorption process of a metal benzoate pyrazine (MII = Rh, Cu). J. Am. Chem. Soc. 132, 3783–3792 (2010).10.1021/ja9091598 ↗
25. Maji, T. K., Mostafa, G., Matsuda, R. & Kitagawa, S. Guest-induced asymmetry in a metal-organic porous solid with reversible single-crystal-to-single-crystal structural transformation. J. Am. Chem. Soc. 127, 17152–17153 (2005).10.1021/ja0561439 ↗
26. van der Lee, A. & Dumitrescu, D. G. Thermal expansion properties of organic crystals: a CSD study. Chem. Sci. 12, 8537–8547 (2021).10.1039/D1SC01076J ↗
27. Katrusiak, A. Lab in a DAC—high-pressure crystal chemistry in a diamond-anvil cell. Acta Crystallogr. B 75, 918–926 (2019).10.1107/S2052520619013246 ↗
28. Kobatake, S., Takami, S., Muto, H., Ishikawa, T. & Irie, M. Rapid and reversible shape changes of molecular crystals on photoirradiation. Nature 446, 778–781 (2007).10.1038/nature05669 ↗
29. Cai, W. et al. Giant negative area compressibility tunable in a soft porous framework material. J. Am. Chem. Soc. 137, 9296–9301 (2015).10.1021/jacs.5b03280 ↗
30. Atwood, J. L., Barbour, L. J., Jerga, A. & Schottel, B. L. Guest transport in a nonporous organic solid via dynamic van der Waals cooperativity. Science 298, 1000–1002 (2002).10.1126/science.1077591 ↗
31. SAINT V8.40B (Bruker AXS Inc., 2001).
32. SADABS-2016/2 (Bruker AXS Inc., 2001).
33. Sheldrick, G. M. A short history of SHELX. Acta Crystallogr. A 64, 112–122 (2008).10.1107/S0108767307043930 ↗
34. Sheldrick, G. M. SHELXT—integrated space-group and crystal-structure determination. Acta Crystallogr. A 71, 3–8 (2015).10.1107/S2053273314026370 ↗
35. Barbour, L. J. X-Seed 4: updates to a program for small-molecule supramolecular crystallography. J. Appl.Crystallogr. 53, 1141–1146 (2020).10.1107/S1600576720007438 ↗
36. Atwood, J. L. & Barbour, L. J. Molecular graphics: from science to art. Cryst. Growth Des. 3, 3–8 (2003).10.1021/cg020063o ↗
37. Sheldrick, G. M. Crystal structure refinement with SHELXL. Acta Crystallogr. C 71, 3–8 (2015).10.1107/S2053229614024218 ↗
38. Connolly, M. L. Solvent-accessible surfaces of proteins and nucleic acids. Science 221, 709–713 (1983).10.1126/science.6879170 ↗
39. Macrae, C. F. et al. Mercury: visualization and analysis of crystal structures. J. Appl. Crystallogr. 39, 453–457 (2006).10.1107/S002188980600731X ↗
40. Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. The Cambridge Structural Database. Acta Crystallogr.B 72, 171–179 (2016).10.1107/S2052520616003954 ↗
41. Bruno, I. J. et al. New software for searching the Cambridge Structural Database and visualizing crystal structures. Acta Crystallogr. B 58, 389–397 (2002).10.1107/S0108768102003324 ↗
42. Benham, M. J. & Ross, D. K. Experimental determination of absorption-desorption isotherms by computer-controlled gravimetric analysis. Z. Phys. Chem. 163, 25–32 (1989).10.1524/zpch.1989.163.Part_1.0025 ↗
43. Fletcher, A. J. & Thomas, K. M. Adsorption and desorption kinetics of n-octane and n-nonane vapors on activated carbon. Langmuir 15, 6908–6914 (1999).10.1021/la9814992 ↗
44. Reid, C. R. & Thomas, K. M. Adsorption of gases on a carbon molecular sieve used for air separation: linear adsorptives as probes for kinetic selectivity. Langmuir 15, 3206–3218 (1999).10.1021/la981289p ↗
45. Fletcher, A. J. & Thomas, K. M. Compensation effect for the kinetics of adsorption/desorption of gases/vapors on microporous carbon materials. Langmuir 16, 6253–6266 (2000).10.1021/la9916528 ↗
46. O’koye, I. P., Benham, M. & Thomas, K. M. Adsorption of gases and vapors on carbon molecular sieves. Langmuir 13, 4054–4059 (1997).10.1021/la961040c ↗