ChemComm
Page 4 of 5
DOI: 10.1039/C9CC04528G
TATA platforms mix perfectly stochastically with the azobenzene-
functionalized TATA molecules.
2
3
K. G. Yager and C. J. Barrett, Journal of Photochemistry and Photobiology A:
Chemistry, 2006, 182, 250–261.
W. R. Browne and B. L. Feringa, in Nanoscience and Technology, Co-Published
with Macmillan Publishers Ltd, UK, 2009, pp. 79–89.
In summary, our study demonstrated that TATA-based
molecules provide a versatile construction kit for the prepara-
tion of structurally well-defined adlayers that exhibit multiple
functional groups. As illustrated here for azobenzene derivatives
and pyridine, the TATA platform enables vertical mounting of
the functional groups at fixed in-plane distances. It exclusively
determines the lateral arrangement in the adlayer, independent
of the attached functional unit. As a consequence, the molecules
are not only homogeneously and statistically distributed in the
adlayer but also have a sufficient free volume for performing ad-
vanced functions, such as the photoswitching of the azobenzene
units. Furthermore, the molecular composition of the mixed
adlayers and thus the fraction of specific functions on the surface
can be varied over a wide range by the concentration ratio in
solution.
4
5
M.-M. Russew and S. Hecht, Advanced Materials, 2010, 22, 3348–3360.
V. S. Miguel, C. G. Bochet and A. del Campo, Journal of the American Chemical
Society, 2011, 133, 5380–5388.
D. Bléger, J. Doki ´c , M. V. Peters, L. Grubert, P. Saalfrank and S. Hecht, The
Journal of Physical Chemistry B, 2011, 115, 9930–9940.
M. Dommaschk, C. Schütt, S. Venkataramani, U. Jana, C. Näther, F. D. Sönnich-
sen and R. Herges, Dalton Trans., 2014, 43, 17395–17405.
M. M. Lerch, M. J. Hansen, W. A. Velema, W. Szymanski and B. L. Feringa,
Nature Communications, 2016, 7, DOI: 10.1038/ncomms12054.
M. Ito, T. X. Wei, P.-L. Chen, H. Akiyama, M. Matsumoto, K. Tamada and Y. Ya-
mamoto, J. Mater. Chem., 2005, 15, 478.
6
7
8
9
0
1
1
1
D. Bléger, F. Mathevet, D. Kreher, A.-J. Attias, A. Bocheux, S. Latil, L. Douillard,
C. Fiorini-Debuisschert and F. Charra, Angew. Chem. Int. Ed., 2011, 50, 6562–
6566.
1
S.-E. Zhu, Y.-M. Kuang, F. Geng, J.-Z. Zhu, C.-Z. Wang, Y.-J. Yu, Y. Luo, Y. Xiao,
K.-Q. Liu, Q.-S. Meng, L. Zhang, S. Jiang, Y. Zhang, G.-W. Wang, Z.-C. Dong and
J. G. Hou, J. Am. Chem. Soc., 2013, 135, 15794–15800.
2
M. Valášek and M. Mayor, Chem. Eur. J., 2017, 23, 13538–13548.
13 L. Sosa-Vargas, E. Kim and A.-J. Attias, Materials Horizons, 2017, 4, 570–583.
14
A. S. Kumar, T. Ye, T. Takami, B.-C. Yu, A. K. Flatt, J. M. Tour and P. S. Weiss,
Nano Letters, 2008, 8, 1644–1648.
Considering that many TATA-based molecules, including various
types of photoswitches (imines, diazocins) and other function-
15 U. Jung, O. Filinova, S. Kuhn, D. Zargarani, C. Bornholdt, R. Herges and O. Mag-
nussen, Langmuir, 2010, 26, 13913–13923.
1
6
7
D. T. Valley, M. Onstott, S. Malyk and A. V. Benderskii, Langmuir, 2013, 29,
11623–11631.
T. Moldt, D. Brete, D. Przyrembel, S. Das, J. R. Goldman, P. K. Kundu, C. Gahl,
R. Klajn and M. Weinelt, Langmuir, 2015, 31, 1048–1057.
3
2–34
alities (e.g. metal complexes),
have been shown to form
1
similar adlayer structures, the concept demonstrated here should
be easily transferable to other binary systems and even adlayers
consisting of three of more different molecular species. Suitable
design of the attached vertical units should allow the realization
of cooperative functions, for example photoswitching of the
chemical reactivity via blocking or activation of a neighbouring
group (Fig. 1a). The latter does not require in-plane order
but only a precise positioning of the different functional groups
relative to each other and thus can be readily realized in stochas-
tically mixed layers as prepared in this work. For example,
18 B. Baisch, D. Raffa, U. Jung, O. M. Magnussen, C. Nicolas, J. Lacour, J. Ku-
bitschke and R. Herges, J. Am. Chem. Soc., 2009, 131, 442–443.
19
20
21
22
23
S. Kuhn, B. Baisch, U. Jung, T. Johannsen, J. Kubitschke, R. Herges and O. Mag-
nussen, Phys. Chem. Chem. Phys., 2010, 12, 4481.
J. Kubitschke, C. Näther and R. Herges, Eur. J. Org. Chem., 2010, 2010, 5041–
5055.
U. Jung, C. Schütt, O. Filinova, J. Kubitschke, R. Herges and O. Magnussen, J.
Phys. Chem. C, 2012, 116, 25943–25948.
F. L. Otte, S. Lemke, C. Schütt, N. R. Krekiehn, U. Jung, O. M. Magnussen and
R. Herges, J. Am. Chem. Soc., 2014, 136, 11248–11251.
H. Jacob, S. Ulrich, U. Jung, S. Lemke, T. Rusch, C. Schütt, F. Petersen, T. Strun-
skus, O. Magnussen, R. Herges and F. Tuczek, Phys. Chem. Chem. Phys., 2014,
16, 22643–22650.
2
2
2
4
5
6
S. Ulrich, U. Jung, T. Strunskus, C. Schütt, A. Bloedorn, S. Lemke, E. Ludwig,
1
3
/3 adlayers, in which Co porphyrins are attached to adsorbed
L. Kipp, F. Faupel, O. Magnussen and R. Herges, Phys. Chem. Chem. Phys., 2015,
3
5
,
access to the metal center may potentially be modified by
17, 17053–17062.
A. Schlimm, R. Löw, T. Rusch, F. Röhricht, T. Strunskus, T. Tellkamp, F. Sön-
nichsen, U. Manthe, O. Magnussen, F. Tuczek and R. Herges, Angew. Chem. Int.
Ed., 2019, 58, 6574–6578.
T. R. Rusch, A. Schlimm, N. R. Krekiehn, B. M. Flöser, F. Röhricht, M. Ham-
merich, I. Lautenschläger, T. Strunskus, R. Herges, F. Tuczek and O. M. Mag-
nussen, J. Phys. Chem. C, 2019, 123, 13720–13730.
S. Lemke, S. Ulrich, F. Claußen, A. Bloedorn, U. Jung, R. Herges and O. M.
Magnussen, Surf. Sci., 2015, 632, 71–76.
B. W. Laursen and F. C. Krebs, Chem. Eur. J., 2001, 7, 1773–1783.
trans-cis isomerization of the azobenzene unit in 1, which would
allow to photoswitch the electrocatalytic O2 reduction reaction.
Furthermore, an even better controlled lateral arrangement of
the different functions may be obtained by combining the plat-
form concept with principles of two-dimensional supramolecular
organization. For planar adsorbate molecules without vertical
functions, assembly of two different species into well-defined
ordered surface arrangements have been achieved using molecu-
lar recognition via hydrogen bonding
via metal atoms3
molecular building blocks
vertically functionalized platforms will require synthesis of
platforms with different lateral ligands that interact with each
other.
2
7
8
2
29 C. Nicolas and J. Lacour, Organic Letters, 2006, 8, 4343–4346.
3
3
0
1
J. Kubitschke, Ph.D. thesis, Kiel University, 2010.
N. Hauptmann, K. Scheil, T. G. Gopakumar, F. L. Otte, C. Schütt, R. Herges and
R. Berndt, J. Am. Chem. Soc., 2013, 135, 8814–8817.
3
6,37
, coordinative bonding
8,39
32 M. Hammerich, T. Rusch, N. R. Krekiehn, A. Bloedorn, O. M. Magnussen and
R. Herges, ChemPhysChem, 2016, 17, 1870–1874.
33 R. Löw, T. Rusch, F. Röhricht, O. M. Magnussen and R. Herges, Beilstein J. Org.
Chem., 2019, DOI: 10.3762/bxiv.2019.11.v1.
, or ionic interactions between charged
4
0
.
Transferring these principles to
34
35
36
37
A. Schlimm, N. Stucke, B. M. Flöser, T. Rusch, J. Krahmer, C. Näther, T. Strun-
skus, O. M. Magnussen and F. Tuczek, Chem. Eur. J., 2018, 24, 10732–10744.
G. Zuo, H. Yuan, J. Yang, R. Zuo and X. Lu, J. Mol. Catal. Chem., 2007, 269,
4
6–52.
R. Madueno, M. T. Räisänen, C. Silien and M. Buck, Nature, 2008, 454, 618–
21.
T. Kudernac, S. Lei, J. A. A. W. Elemans and S. D. Feyter, Chem. Soc. Rev., 2009,
8, 402–421.
6
We gratefully acknowledge financial support by the Deutsche
Forschungsgemeinschaft (DFG) via the collaborative research
centre SFB677, project B09.
3
38 S. Stepanow, M. Lingenfelder, A. Dmitriev, H. Spillmann, E. Delvigne, N. Lin,
X. Deng, C. Cai, J. V. Barth and K. Kern, Nature Materials, 2004, 3, 229–233.
3
4
9
0
D. P. Goronzy, M. Ebrahimi, F. Rosei, Arramel, Y. Fang, S. D. Feyter, S. L. Tait,
Conflicts of interest
There are no conflicts to declare.
C. Wang, P. H. Beton, A. T. S. Wee, P. S. Weiss and D. F. Perepichka, ACS Nano,
2018, 12, 7445–7481.
K. Cui, K. S. Mali, D. Wu, X. Feng, K. Müllen, M. Walter, S. D. Feyter and S. F. L.
Mertens, Small, 2017, 13, 1702379.
Notes and references
1
T. Ikeda and O. Tsutsumi, Science, 1995, 268, 1873–1875.
4
|
1–4