TY - JOUR
T1 - Guest Exchange through Facilitated Transport in a Seemingly Impenetrable Hydrogen-Bonded Framework
AU - Li, Yuantao
AU - Handke, Marcel
AU - Chen, Yu Sheng
AU - Shtukenberg, Alexander G.
AU - Hu, Chunhua T.
AU - Ward, Michael D.
N1 - Funding Information:
We acknowledge the support of the Materials Research Science and Engineering Center (MRSEC) Program of the National Science Foundation under award number DMR-1420073, the National Science Foundation through DMR-1308677, and the NSF Chemistry Research Instrumentation and Facilities Program (CHE-0840277). We also are grateful to A. Martin, T. Adachi, and M. Tan (NYU) and M. Olmstead (UC Davis) for helpful comments. Synchrotron X-ray data were collected at the ChemMatCARS Sector 15 at the Advanced Photon Source (APS), which is principally supported by the Divisions of Chemistry (CHE) and Materials Research (DMR), National Science Foundation, under grant number NSF/CHE-1346572. Use of the APS, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science by Argonne National Laboratory, was supported by the U.S. DOE under contract no. DE-AC02-06CH11357.
Publisher Copyright:
Copyright © 2018 American Chemical Society.
PY - 2018/10/10
Y1 - 2018/10/10
N2 - A new inclusion compound consisting of a guanidinium 1,3,5-tri(4-sulfophenyl)benzene (G3TSPHB) host framework containing isophorone guests that surround isolated and seemingly inaccessible pockets was amenable to guest exchange with hexafluorobenzene (HFB) through a single crystal-single crystal transformation (SCSCT). Single-crystal X-ray diffraction of intermediate transformation states, from the parent compound G3TSPHB·(isophorone)3.7·(methanol)5.4 to the final state G3TSPHB·(isophorone)3.1·(HFB)2·(methanol)2, indicated a crystal symmetry change from monoclinic to hexagonal prior to full incorporation of HFB. Optical microscopy during the SCSCT revealed the formation of lamellae, which expanded and then coalesced into a single crystal when the phase transformation was complete. In situ Raman microscopy revealed changes in the orientation of isophorone guests during the transformation that suggested a pathway for HFB entry into the host cavities. The SCSCT occurs more rapidly than expected on the basis of simple diffusion, consistent with facilitated transport along the lamellae interfaces and a reduction in the length scale for guest exchange.
AB - A new inclusion compound consisting of a guanidinium 1,3,5-tri(4-sulfophenyl)benzene (G3TSPHB) host framework containing isophorone guests that surround isolated and seemingly inaccessible pockets was amenable to guest exchange with hexafluorobenzene (HFB) through a single crystal-single crystal transformation (SCSCT). Single-crystal X-ray diffraction of intermediate transformation states, from the parent compound G3TSPHB·(isophorone)3.7·(methanol)5.4 to the final state G3TSPHB·(isophorone)3.1·(HFB)2·(methanol)2, indicated a crystal symmetry change from monoclinic to hexagonal prior to full incorporation of HFB. Optical microscopy during the SCSCT revealed the formation of lamellae, which expanded and then coalesced into a single crystal when the phase transformation was complete. In situ Raman microscopy revealed changes in the orientation of isophorone guests during the transformation that suggested a pathway for HFB entry into the host cavities. The SCSCT occurs more rapidly than expected on the basis of simple diffusion, consistent with facilitated transport along the lamellae interfaces and a reduction in the length scale for guest exchange.
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U2 - 10.1021/jacs.8b07065
DO - 10.1021/jacs.8b07065
M3 - Article
C2 - 30264567
AN - SCOPUS:85054246135
VL - 140
SP - 12915
EP - 12921
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 40
ER -