Molecular dynamics simulation of amphiphilic bistable [2]rotaxane Langmuir monolayers at the air/water interface

Seung Soon Jang, Yun Hee Jang, Yong Hoon Kim, William A. Goddard*, Jang Wook Choi, James R. Heath, Bo W. Laursen, Amar H. Flood, J. Fraser Stoddart, Kasper Nørgaard, Thomas Bjørnholm

*Corresponding author for this work

Research output: Contribution to journalArticle

177 Scopus citations


Bistable [2]rotaxanes display controllable switching properties in solution, on surfaces, and in devices. These phenomena are based on the electrochemically and electrically driven mechanical shuttling motion of the ring-shaped component, cyclobis(paraquat-p-phenylene) (CBPQT4+), between a monopyrrolotetrathiafulvalene (mpTTF) unit and a 1,5-dioxynaphthalene (DNP) unit located along a dumbbell component. The most stable state of the rotaxane (CBPQT4+ @ mpTTF) is that in which the CBPQT4+ ring encircles the mpTTF unit, but a second less favored metastable co-conformation with the CBPQT4+ ring surrounding the DNP (CBPQT 4+ @ DNP) can be formed experimentally. For both co-conformations of an amphiphilic bistable [2]rotaxane, we report here the structure and surface pressure-area isotherm of a Langmuir monolayer (LM) on a water subphase as a function of the area per molecule. These results from atomistic molecular dynamics (MD) studies are validated by comparing with experiments based on similar amphiphilic rotaxanes. For both co-conformations, we found that as the area per molecule increases the thickness of the LM decreases while the molecular tilt increases. Both co-conformations led to similar LM thicknesses at the same packing area. From the simulated LM systems, we calculated the electron density profiles of the monolayer as a function of area per molecule, which show good agreement with experimental analyses from synchrotron X-ray reflectivity measurements of related systems. Decomposing the overall electron density profiles into component contributions, we found distinct differences in molecular packing in the film depending upon the co-conformation. Thus we find that the necessity of allowing the tetracationic ring to become solvated by water leads to differences in the structures for the two co-conformations in the LM. At the same packing area, the value of the overall tilt angle does not seem to be sensitive to whether the CBPQT4+ ring is encircling the mpTTF or the DNP unit. However, the conformation of the dumbbell does depend on the location of the CBPQT4+ ring, which is reflected in the segmental tilt angles of the mpTTF and DNP units. Using the Kirkwood-Buff formula in conjunction with MD calculations, we find the surface pressure-area isotherms for each co-conformation in which the CBPQT4+ @ mpTTF form has smaller surface tension and therefore larger surface pressure than the CBPQT4+ @ DNP at the same packing area, differences that decreases with increasing area per molecule, which is verified experimentally.

Original languageEnglish (US)
Pages (from-to)14804-14816
Number of pages13
JournalJournal of the American Chemical Society
Issue number42
StatePublished - Nov 1 2005

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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    Jang, S. S., Jang, Y. H., Kim, Y. H., Goddard, W. A., Choi, J. W., Heath, J. R., Laursen, B. W., Flood, A. H., Stoddart, J. F., Nørgaard, K., & Bjørnholm, T. (2005). Molecular dynamics simulation of amphiphilic bistable [2]rotaxane Langmuir monolayers at the air/water interface. Journal of the American Chemical Society, 127(42), 14804-14816.