We demonstrate that the Van der Waals interactions in plane are important to control molecular self-assembly structure as well their phase transition. Using precise chemical modification to mediate such in-plane cohesive interactions, we observed the spontaneous formations of 2D order or disorder molecular self-assembly structures, as well their order-disorder phase transitions by annealing. Interestingly, we identified that the side alkyl chains stand up at surfaces and form the ‘locked’ pairs/windmill structures. Moreover, we realized the covalent coupling based on ethynyl functionality before molecular desorption from metal surfaces, by enhancing the in-plane interactions.

1.
G. M.
Whitesides
and
B.
Grzybowski
,
Science
295
,
2418
(
2002
).
2.
S. D.
Feyter
and
F. C.
De Schryver
,
J. Phys. Chem. B
109
,
4290
(
2005
).
3.
S. M.
Barlow
and
R.
Raval
,
Surf. Sci. Rep.
50
,
201
(
2003
).
4.
J. A.
Theobald
,
N. S.
Oxtoby
,
M. A.
Phillips
,
N. R.
Champness
, and
P. N.
Beton
,
Nature
424
,
1029
(
2003
).
5.
S.
Clair
,
S.
Pons
,
A. P.
Seitsonen
,
H.
Brune
,
K.
Kern
, and
J. V.
Barth
,
J. Phys. Chem. B
108
,
14585
(
2004
).
6.
N. A.
Wasio
,
R. C.
Quardokus
,
R. P.
Forrest
,
C. S.
Lent
,
S. A.
Corcelli
,
J. A.
Christie
,
K. W.
Henderson
, and
S. A.
Kandel
,
Nature
507
,
86
(
2014
).
7.
K. A.
Fichthorn
and
R. A.
Miron
,
Phys. Rev. Lett.
89
,
196103
(
2002
).
8.
H. Y.
Gao
,
P. A.
Held
,
M.
Knor
,
C. M.
Lichtenfeld
,
J.
Neugebauer
,
A.
Studer
, and
H.
Fuchs
,
J. Am. Chem. Soc.
136
,
9658
(
2014
).
9.
J. A. A. W.
Elemans
,
S.
Lei
, and
S. D.
Feyter
,
Angew. Chem. Int. Ed.
48
,
7298
(
2009
).
10.
H.
Ascolani
,
M. W.
Meijden
,
L. J.
Cristina
,
J. E.
Gayone
,
R. M.
Kellogg
,
J. D.
Fuhr
, and
M.
Lingenfelder
,
Chem. Commun.
50
,
13907
(
2014
).
11.
J.
Cechal
,
C. S.
Kley
,
T.
Kumagai
,
F.
Schramm
,
M.
Ruben
,
S.
Stepanow
, and
K.
Kern
,
Chem. Commun.
50
,
9973
(
2014
).
12.
H.
Cun
,
Y.
Wang
,
S.
Du
,
L.
Zhang
,
L.
Zhang
,
B.
Yang
,
X.
He
,
Y.
Wang
,
X.
Zhu
,
Q.
Yuan
 et al,
Nano Lett.
12
,
1229
(
2012
).
13.
D.
Mössinger
,
D.
Chaudhuri
,
T.
Kudernac
,
S.
Lei
,
S. D.
Feyter
,
J. M.
Lupton
, and
S.
Höger
,
J. Am. Chem. Soc.
132
,
1410
(
2010
).
14.
H. Y.
Gao
,
H.
Wagner
,
D.
Zhong
,
J. H.
Franke
,
A.
Studer
, and
H.
Fuchs
,
Angew. Chem. Int. Ed.
52
,
4024
(
2013
).
15.
Y. Q.
Zhang
,
N.
Kepcija
,
M.
Kleinschrodt
,
K.
Diller
,
S.
Fischer
,
A. C.
Papageorgiou
,
F.
Allegretti
,
J.
Björk
,
S.
Klyatskaya
,
F.
Klappenberger
 et al,
Nat. Commun.
3
,
1286
(
2012
).
16.
N.
Kepcija
,
Y. Q.
Zhang
,
M.
Kleinschrodt
,
J.
Bjork
,
S.
Klyatskaya
,
F.
Klappenberger
,
M.
Ruben
, and
J. V.
Barth
,
J. Phys. Chem. C
117
,
3987
(
2013
).
17.
L.
Askadskaya
and
J. P.
Rabe
,
Phys. Rev. Lett.
69
,
1395
(
1992
).
18.
M. O.
Blunt
,
J.
Adisoejoso
,
K.
Tahara
,
K.
Katayama
,
M. V.
Auweraer
,
Y.
Tobe
, and
S. D.
Feyter
,
J. Am. Chem. Soc.
135
,
12068
(
2013
).
19.
S.
Ahn
and
A. J.
Matzger
,
J. Am. Chem. Soc.
132
,
11364
(
2010
).
20.
R.
Gutzler
,
T.
Sirtl
,
J. F.
Dienstmaier
,
K.
Mahata
,
W. M.
Heckl
,
M.
Schmittel
, and
M.
Lackinger
,
J. Am. Chem. Soc.
132
,
5084
(
2010
).
21.
See supplementary material at http://dx.doi.org/10.1063/1.4907777 for the dynamical movements of terminal carbons of C4 groups.

Supplementary Material

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