Frath, Denis

Hirose, Takashi

Imaizumi, Yohei

Matsuda, Kenji

Sakano, Takeshi

Yokoyama, Soichi

English

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HAL Id: hal-02103593
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Cooperativity Analysis of the Open-, Closed-and
Annulated-Isomers of Diarylethene that form 2-D
Ordering at the Liquid/Solid Interface and their
Photochemical Interchanges
Denis Frath, Takeshi Sakano, Yohei Imaizumi, Soichi Yokoyama, Takashi
Hirose, Kenji Matsuda
To cite this version:
Denis Frath, Takeshi Sakano, Yohei Imaizumi, Soichi Yokoyama, Takashi Hirose, et al.. Cooperativity
Analysis of the Open-, Closed-and Annulated-Isomers of Diarylethene that form 2-D Ordering at
the Liquid/Solid Interface and their Photochemical Interchanges. Annual Meeting of the Japanese
Photochemistry Association, Oct 2014, Sapporo, Japan. ￿hal-02103593￿
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Photoisomerization 
 
Irradiation (λ=365 nm) of 1o solution ([1o] = 29.4 µM) 
 
Ratio Φo→c : Φc→o : Φc→a is 1 : 0.047 : 0.001 
 Φo→c = 0.59 (reported)
11; Φc→o = 0.028; Φc→a = 0.0006 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Cooperativity Analysis of the Open-, Closed- and Annulated-
Isomers of Diarylethene that form 2-D Ordering at the 
Liquid/Solid Interface and their Photochemical Interchanges 
Denis Frath, Takeshi Sakano, Yohei Imaizumi, Soichi Yokoyama, Takashi Hirose, Kenji Matsuda 
Kyoto University, Graduate School of Engineering 
Dr. Denis Frath, JSPS postdoctoral fellow 
Kyoto University, Graduate School of Engineering 
Email: dfrath@sbchem.kyoto-u.ac.jp 
Website: http://www.sbchem.kyoto-u.ac.jp/matsuda-lab 
Personal page: researchgate.net/profile/Denis_Frath 
Phone: 075 383 2746 
Contact 
1. J. V. Barth, G. Costantini, K. Kern, Nature 2005, 437, 671–679 
2. T. Kudernac, S. Lei, J. A. A. W. Elemans, S. De Feyter, Chem. Soc. Rev. 2009, 38, 402–421 
3. K. S. Mali, J. Adisoejoso, E. Ghijsens, I. De Cat, S. De Feyter, Acc. Chem. Res. 2012, 45, 1309–1320 
4. A. G. Slater (nee Phillips), P. H. Beton, N. R. Champness, Chem. Sci. 2011, 2, 1440–1448 
5. S. De Feyter, F. C. De Schryver, Chem. Soc. Rev. 2003, 32, 139–150 
6. M. Irie, Chem. Rev. 2000, 100, 1685–1716. 
7. K. Matsuda, M. Irie, J. Photochem. Photobiol. C 2004, 5, 169 – 182 
8. R. Arai, S. Uemura, M. Irie, K. Matsuda, J. Am. Chem. Soc. 2008 
9. S. Yokoyama, T. Hirose, K. Matsuda, Chem. Commun. 2014, 50, 5964–5966 
10. T. Sakano, Y. Imaizumi, T. Hirose, K. Matsuda, Chem. Lett. 2013, 42, 1537–1539 
11. M. Irie, T. Lifka, S. Kobatake, N. Kato, J. Am. Chem. Soc. 2000, 122, 4871–4876 
12. D. Zhao, J. S. Moore, Org. Biomol. Chem. 2003, 1, 3471–3491 
13. T. F. A. De Greef, M. M. J. Smulders, M. Wolffs, A. P. H. J. Schenning, R. P. Sijbesma, E. W. Meijer, Chem. Rev. 2009, 109, 5687–5754 
14. R. Heinz, A. Stabel, F. C. De Schryver, J. P. Rabe, J. Phys. Chem. 1995, 99, 505–507 
15. G. M. Florio, J. E. Klare, M. O. Pasamba, T. L. Werblowsky, M. Hyers, B. J. Berne, M. S. Hybertsen, C. Nuckolls, G. W. Flynn, Langmuir 2006, 22, 10003–10008 
 
References 
Control over molecular nanostructure: “bottom-up” strategy1 for molecular electronic devices  
 
2-D supramolecular self-assembly at interfaces widely studied2-4 
 
Scanning Tunneling Microscopy (STM):  
efficient tool for the characterization of  
Self-assembled Monolayers (SAM)5 
 
Light as external stimulus: require 
photo-responsive material 
 
Diarylethene: high thermal stability of  
each isomer,high fatigue resistance6,7 
 
Diarylethene-pyrene: photoinduced  
reversible control between 2 orderings8 
 
Stabilization by H-bond network9,10 
 
Ordering γ favored / ordering β:  
after UV, β was never observed10 
Introduction 
Results and Discussions 
 
Adsorption processes were modelized: open-
isomer 1o is isodesmic,  closed-isomer 1c is 
cooperative and annulated-isomer 1a has a very 
high affinity for HOPG (Ke > 10
6) 
 
This work highlighted the existence of mix-
crystals 1o/1c and the “Induced cooperativity” on 
formation of ordering α by addition of 1c. 
 
A better understanding of photochemical 
interchanges became possible: SAM obtained from 
irradiated solution can be predicted by the model 
 
The STM analysis of the in-situ irradiation suggest 
a modification of photochomic properties at the 
octanoic acid/HOPG interface 
Conclusions 
Figure 1. Open-, closed- and annulated-isomers and their 2-D orderings 
SAM obtained from irradiated solutions 
 
Irradiation (λ=365 nm) of 1o solution ([1o] = 28.7 µM) 
 
Exact composition (UV-Vis): calculated fractional 
coverage values (cooperative model) 
 
Experimental fractional coverage values (STM) 
 
Experimental θβ > Calculated θβ.;  α not observed 
 
Co-crystalization ? 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Bi-component adsorption parameters 
 
 
 
 
 
 
 
 
 
 
 
 
Modification of adsorption properties for  
bi-component systems: mix-crystals 1o/1c 
 
Depending of the ratio: ordering α or 
ordering β, both never observed together 
 
Induced cooperativity on the formation 
of α by addition of 1c to solutions of 1o 
Calc. θα Exp. θα Calc. θβ Exp. θβ Calc. θγ
* Exp. θγ 
5 min 0.40 0 0.08 0.35 0.09 0 
15 min 0.33 0 0.02 0.18 0.26 0.32 
45 min 0.21 0 0 0.005 0.87 0.79 
In-situ irradiation of SAM 
 
In-situ irradiation of SAM  
obtained from 1o solution  
([1o] = 30.0 µM) 
 
Progressive disappearance 
of ordering α 
 
Replacement by ordering γ 
 
After about 1h: only  
ordering γ 
 
Reorganization: Ostwald 
ripening14,15 
 
Figure 3: ratio in favor of β 
but it was never observed 
 
Modification of photochromic 
properties at the interface ? 
Table 2. Calculated and experimental fractional coverage 
Mono-component adsorption parameters 
 
Cooperative supramolecular polymer12-13 
 
Cooperative model at the octanoic acid/highly 
oriented pyrolytic graphite (HOPG) interface10 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Compound Ke (M
−1) Kn (M
−1) σ 
1o 6.7 ± 0.2 x 104 6.7 ± 0.2 x 104 1 
1c 6.5 ± 0.3 x 104 ≤ 6.5 ± 0.3 x 10-2 ≤ 10−6 
1a  1.5 ± 0.5 x  106 ≤ 1.5 ± 0.5 ≤ 10−6 
Table 1. Best-fitting adsorption parameters for 1o, 1c and 1a 
Figure 4. Concentration dependence of the surface coverage 
Figure 3. Evolution of concentrations  upon irradiation with UV light 
Figure 9. STM images of the in-situ photoirradiation 
Figure 5. STM image from an irradiated solution of 1o 
*Calculated using cooperative parameters 
Figure 6. [1o] dependence of the surface coverage 
Figure 7. [1c] dependence of the surface coverage 
Figure 8.  1o/1c ratio dependence of  Ke 
Figure 2. Absorption spectra in octanoic acid 


Cooperativity Analysis of the Open-, Closed-and Annulated-Isomers of Diarylethene that form 2-D Ordering at the Liquid/Solid Interface and their Photochemical Interchanges

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Cooperativity Analysis of the Open-, Closed-and Annulated-Isomers of Diarylethene that form 2-D Ordering at the Liquid/Solid Interface and their Photochemical Interchanges

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