Journal of
Materials Chemistry C
PAPER
A cross-dipole stacking molecule of an
anthracene derivative: integrating optical and
electrical properties†
Cite this: J. Mater. Chem. C, 2015,
, 3068
3
ab
bc
a
d
ab
Jie Liu, Lingqiang Meng, Weigang Zhu, Congcong Zhang, Hantang Zhang,
ab
ab
ab
a
c
Yifan Yao, Zongrui Wang, Ping He, Xiaotao Zhang, Ying Wang,
Yonggang Zhen, Huanli Dong, Yuanping Yi and Wenping Hu*
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ad
Received 27th December 2014,
Accepted 4th February 2015
Cross-dipole stacking has been addressed as a preferred motif for solid state emission, but inefficient for
charge transport. Here we synthesize a new anthracene derivative, which adopts cross-stacking in the
2
À1 À1
solid state with a solid state fluorescence up to 77.3% and a hole mobility of 1.47 cm
V
s ,
DOI: 10.1039/c4tc02964j
integrating optical and electrical properties successfully. As far as we know, it is the first report of
organic field-effect transistors based on cross-dipole stacking molecules.
www.rsc.org/MaterialsC
Relationships between molecular packing and chemical–physical anthracene derivatives as the candidates because anthracene itself
1
2,13
properties have been one of the most studied subjects in organic is characterized with both optical and electrical properties.
Up
1–3
electronics. Molecular packing modes can be generally classified to now, anthracene derivatives with high charge transfer properties
4
5,6
14–16
into H-aggregation, J-aggregation and X-aggregation (cross- have been mainly based on 2,6-substitution,
and highly
7–9
dipole stacking). For H-aggregation, usually strong molecular fluorescent materials are addressed for 9,10-substituted anthra-
17,18
p–p interactions are expected, which facilitate charge transport cene derivatives.
We believe that if bulky groups are introduced
10
efficiently but are inefficient for emission. Compared with into the molecule skeleton, the molecular distance of the
H-aggregation, the dipole–dipole interactions in J-aggregation p-conjugation could be enlarged, which might contribute to
are relatively smaller, which might ensure emission properties as the minimization of the quenching of emission in solid states just
6
well as part of charge transport properties. X-aggregation, which like in diluted solution or the dispersed state in a polymer matrix.
has been studied both theoretically and experimentally, is the
A new compound, (2,6-diphenylanthracene-9,10-diyl)bis(ethyne-
most effective in preventing luminescence quenching in the solid 2,1-diyl)bis(triethylsilane) (TES-DPA), is synthesized, which is an
7,11
state.
For example, a distyrylbenzene derivative (trans-DPDSB) anthracene derivative with an enlarged p-conjugation along the
with a cross stacking structure was found to exhibit pure blue long axis, and bulky substitution at the short axis. Single crystal
7
emission, and an anthracene derivative of BDPVA was charac- analysis revealed that TES-DPA adopts a cross dipole stacking
8
terized with cross stacking and high fluorescence too. However, structure. Moreover, a fluorescence quantum yield (F
F
) of 77.3%
no reports on charge transport properties of such molecules have is determined for the crystalline state of TES-DPA and a mobility of
2
À1 À1
been recorded because of the poor intermolecular overlap.
1.47 cm V
s
is obtained for its single crystal OFET devices.
In order to integrate optical and electrical properties of one
organic material simultaneously, we carry out this study and select from 2,6-diaminoanthracene-9,10-dione, Sandmeyer reaction
The synthesis of TES-DPA is shown in Scheme 1. Starting
1
9
2
0
and Suzuki coupling reaction took place successively to
get 2,6-diphenylanthracene-9,10-dione, and further addition
of triethylsilylethynyllithium followed by deoxygenation with
a
Beijing National Laboratory for Molecular Science, Key Laboratory of Organic
Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190,
China. E-mail: huwp@iccas.ac.cn
21
stannous chloride gave the target molecule with 46% yield.
b
c
Single crystals of TES-DPA are grown by slow evaporation
from chlorobenzene solution. A crystal with a size of 0.24 mm Â
0.12 mm  0.10 mm is selected for single crystal analysis. As
shown in Fig. 1A, isomers with different conformations coexist
in the solid state (M1, M2, M3). Varied twisted angles are
demonstrated for the substituted benzene rings of the three
isomers. For M1, the two benzene rings are found with torsion
angles of 28.461 and 43.071, and the benzene rings in M2 and
University of the Chinese Academy of Sciences, Beijing 100190, China
Key Laboratory of Photochemical Conversion and Optoelectronic Materials,
Technical Institute of Physics and Chemistry, Chinese Academy of Sciences,
Beijing, 100190, People’s Republic of China
d
Collaborative Innovation Center of Chemical Science and Engineering (Tianjin) &
School of Science, Tianjin University, Tianjin 300072, China
†
Electronic supplementary information (ESI) available: Experiments, synthesis
procedures, crystallographic information, time-resolved fluorescence, current
and power efficiency curves of the OLED device. See DOI: 10.1039/c4tc02964j
3068 | J. Mater. Chem. C, 2015, 3, 3068--3071
This journal is ©The Royal Society of Chemistry 2015