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note
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2H NMR spectra for 1 show a sharp decrease in structural water mobility in the temperatures range from 253 to 223 K. Accordingly, DSC measurements for 1 show a broad endotherm in the temperature interval, 197-273 K, indicating a higher organization of this type of water molecule when the temperature is lowered (Supporting Information).
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For a general methodology for the synthesis of unsaturated homologues, see: Pérez-Hernández, N.; Fehles, M.; Pérez, C.; Pérez, R.; Rodríguez, M. L.; Foces-Foces, C.; Martín, J. D. J. Org. Chem. 2006, 71, 1139-1151.
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note
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2O is isomorphous with that of the ethyl homologue 1 and has been determined at 293, 170, and 115 K. There is no evidence for phase transition when cooling the sample, and the differences are due to the thermal motion which mainly affects the disordered water molecules inside the pore. The main differences between both structures can be attributed to the size of the monomer appendages, larger in 2 than in 1, that affects the inner size of the pore by narrowing the diameter to 4.2-6.5 Å. The water molecule inside the pore in 2 is disordered over three positions. The one with major occupancy factor (ca. 75% of the cells) and those symmetry-related by the -3 axis form a slightly distorted octahedron. The two positions with minor occupancy factors account for the remaining 25%, one is on the octahedron center while the second one is also positioned on the -3 axis but off the octahedron (Supporting Information).
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