Cooperative Self-assembly of Photochromic Diarylethenes at Liquid/Solid Interface and Highly Sensitive Photoinduced Transformation of the Ordering

  • Kenji Matsuda
  • Takashi Hirose
  • Soichi Yokoyama
  • Denis Frath


In this chapter, self-assembly of photochromic diarylethene at liquid/solid interface and photoinduced transformation of the ordering are described. Using scanning tunneling microscopy, the process of assembly can be studied at the molecular resolution. By the measurement of concentration dependence of surface coverage and the introduction of cooperative adsorption model, the degree of cooperativity in the self-assembly process can be evaluated and the guiding principle for highly sensitive photoresponsive system can be obtained. It is demonstrated that the precise control of the self-assembly process on 2D surface becomes possible by the careful design of the molecular structure.


Photochromism Diarylethene Scanning tunneling microscopy Self-assembly Cooperativity 



This research was supported by the Funding Program for Next Generation World-Leading Researchers (NEXT program, no. GR062) and a Grant-in-Aid for Scientific Research on Innovative Areas “Photosynergetics” JSPS KAKENHI Grant Number JP26107008 from the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan.


  1. 1.
    Barth JV, Costantini G, Kern K (2005) Engineering atomic and molecular nanostructures at surfaces. Nature 437:671–679CrossRefGoogle Scholar
  2. 2.
    Joachim C, Ratner MA (2005) Molecular electronics: some views on transport junctions and beyond. Proc Natl Acad Sci USA 102:8801–8802CrossRefGoogle Scholar
  3. 3.
    Moth-Poulsen K, Bjørnholm T (2009) Molecular electronics with single molecules in solid-state devices. Nat Nanotechnol 4:551–556CrossRefGoogle Scholar
  4. 4.
    Feringa BL, Browne WR (eds) (2011) Molecular switches, 2nd edn. Wiley-VCH, WeinheimGoogle Scholar
  5. 5.
    Irie M, Fukaminato T, Matsuda K, Kobatake S (2014) Photochromism of diarylethene molecules and crystals: memories, switches, and actuators. Chem Rev 114:12174–12277CrossRefGoogle Scholar
  6. 6.
    Rabe JP, Buchholz S (1991) Commensurability and mobility in two-dimensional molecular patterns on graphite. Science 253:424–427CrossRefGoogle Scholar
  7. 7.
    Palma CA, Cecchini M, Samorì P (2012) Predicting self-assembly: from empirism to determinism. Chem Soc Rev 41:3713–3730CrossRefGoogle Scholar
  8. 8.
    Elemans JAAW, Lei S, De Feyter S (2009) Molecular and supramolecular networks on surfaces: from two-dimensional crystal engineering to reactivity. Angew Chem Int Ed 48:7298–7332CrossRefGoogle Scholar
  9. 9.
    De Feyter S, De Schryver FC (2003) Two-dimensional supramolecular self-assembly probed by scanning tunneling microscopy. Chem Soc Rev 32:139–150CrossRefGoogle Scholar
  10. 10.
    Xue Y, Zimmt MB (2012) Patterned monolayer self-assembly programmed by side chain shape: four-component gratings. J Am Chem Soc 134:4513–4516CrossRefGoogle Scholar
  11. 11.
    Nath KG, Ivasenko O, MacLeod JM, Miwa JA, Wuest JD, Nanci A, Perepichka DF, Rosei F (2007) Crystal engineering in two dimensions: an approach to molecular nanopatterning. J Phys Chem C 111:16996–17007CrossRefGoogle Scholar
  12. 12.
    Zhang X, Zeng Q, Wang C (2013) Molecular templates and nano-reactors: two-dimensional hydrogen bonded supramolecular networks on solid/liquid interfaces. RSC Adv. 3:11351–11366CrossRefGoogle Scholar
  13. 13.
    Cyr DM, Venkataraman B, Flynn GW (1996) STM Investigations of organic molecules physisorbed at the liquid-solid interface. Chem Mater 8:1600–1615CrossRefGoogle Scholar
  14. 14.
    Tahara K, Katayama K, Blunt MO, De Feyter S, Tobe Y (2014) Functionalized surface-confined pores: guest binding directed by lateral noncovalent interactions at the solid-liquid interface. ACS Nano 8:8683–8694CrossRefGoogle Scholar
  15. 15.
    Xu L, Miao XR, Ying X, Deng WL (2012) Two-dimensional self-assembled molecular structures formed by the competition of van der Waals forces and dipole–dipole interactions. J Phys Chem C 116:1061–1069CrossRefGoogle Scholar
  16. 16.
    Yang Y, Wang C (2009) Solvent effects on two-dimensional molecular self-assemblies investigated by using scanning tunneling microscopy. Curr Opin Colloid Interface Sci 14:135–147CrossRefGoogle Scholar
  17. 17.
    Destoop I, Ghijsens E, Katayama K, Tahara K, Mali KS, Tobe Y, De Feyter S (2012) Solvent-induced homochirality in surface-confined low-density nanoporous molecular networks. J Am Chem Soc 134:19568–19571CrossRefGoogle Scholar
  18. 18.
    Xu L, Miao X, Zha B, Deng W (2012) Self-assembly polymorphism: solvent-responsive two-dimensional morphologies of 2,7-ditridecyloxy-9-fluorenone by scanning tunneling microscopy. J Phys Chem C 116:16014–16022CrossRefGoogle Scholar
  19. 19.
    Takami T, Mazur U, Hipps KW (2009) Solvent-induced variations in surface structure of a 2,9,16,23-tetra-tert-butyl-phthalocyanine on graphite. J Phys Chem C 113:17479–17483CrossRefGoogle Scholar
  20. 20.
    Blunt MO, Adisoejoso J, Tahara K, Katayama K, Van der Auweraer M, Tobe Y, De Feyter S (2013) Temperature-induced structural phase transitions in a two-dimensional self-assembled network. J Am Chem Soc 135:12068–12075CrossRefGoogle Scholar
  21. 21.
    Song W, Martsinovich N, Heckl WM, Lackinger M (2013) Born-Haber cycle for monolayer self-assembly at the liquid-solid interface: assessing the enthalpic driving force. J Am Chem Soc 135:14854–14862CrossRefGoogle Scholar
  22. 22.
    Miyake Y, Nagata T, Tanaka H, Yamazaki M, Ohta M, Kokawa R, Ogawa T (2012) Entropy-controlled 2D supramolecular structures of N, N′-bis(n-alkyl)-naphthalenediimides on a HOPG surface. ACS Nano 6:3876–3887CrossRefGoogle Scholar
  23. 23.
    Gutzler R, Sirtl T, Dienstmaier JF, Mahata K, Heckl WM, Schmittel M, Lackinger M (2010) Reversible phase transitions in self-assembled monolayers at the liquid-solid interface: temperature-controlled opening and closing of nanopores. J Am Chem Soc 132:5084–5090CrossRefGoogle Scholar
  24. 24.
    Ciesielski A, Palma CA, Bonini M, Samorì P (2010) Towards supramolecular engineering of functional nanomaterials: pre-programming multi-component 2D self-assembly at solid-liquid interfaces. Adv Mater 22:3506–3520CrossRefGoogle Scholar
  25. 25.
    Zhang XM, Zeng QD, Wang C (2013) Reversible phase transformation at the solid-liquid Interface: STM reveals. Chem Asian J 8:2330–2340CrossRefGoogle Scholar
  26. 26.
    Arai R, Uemura S, Irie M, Matsuda K (2008) Reversible photoinduced change in molecular ordering of diarylethene derivatives at a solution-HOPG interface. J Am Chem Soc 130:9371–9379CrossRefGoogle Scholar
  27. 27.
    Sakano T, Imaizumi Y, Hirose T, Matsuda K (2013) Formation of two-dimensional ordering of diarylethene annulated isomer upon in situ UV irradiation at the liquid/HOPG interface. Chem Lett 42:1537–1539CrossRefGoogle Scholar
  28. 28.
    Yokoyama S, Hirose T, Matsuda K (2014) Phototriggered formation and disappearance of surface-confined self-assembly composed of photochromic 2-thienyl-type diarylethene: a cooperative model at the liquid/solid interface. Chem Commun 50:5964–5966CrossRefGoogle Scholar
  29. 29.
    Martin RB (1996) Comparisons of indefinite self-association models. Chem Rev 96:3043–3064CrossRefGoogle Scholar
  30. 30.
    Yokoyama S, Hirose T, Matsuda K (2015) Effects of alkyl chain length and hydrogen bonds on the cooperative self-assembly of 2-thienyl-type diarylethenes at a liquid/highly oriented pyrolytic graphite (HOPG) interface. Chem Eur J 21:13569–13576CrossRefGoogle Scholar
  31. 31.
    Frath D, Sakano T, Imaizumi Y, Yokoyama S, Hirose T, Matsuda K (2015) Diarylethene self-assembled monolayers: cocrystallization and mixing-induced cooperativity highlighted by scanning tunneling microscopy at the liquid/solid interface. Chem Eur J 21:11350–11358CrossRefGoogle Scholar

Copyright information

© Springer Japan KK 2017

Authors and Affiliations

  • Kenji Matsuda
    • 1
  • Takashi Hirose
    • 1
  • Soichi Yokoyama
    • 1
  • Denis Frath
    • 1
  1. 1.Department of Synthetic Chemistry and Biological Chemistry, Graduate School of EngineeringKyoto University, KatsuraNishikyo-ku, KyotoJapan

Personalised recommendations