10.1002/anie.202014108
Angewandte Chemie International Edition
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to an Ag wire coated with AgCl as pseudo-reference electrode. c) and d)
Transfer characteristics measured in the saturated regime of operation (Vg = Vsd
= −60 V) for crystal 4a and 4b. Inset: optical microscopy image of devices. e)
and f) molecular packing and centroid distance between crystals for 4a and 4b.
observations suggested ABT derivatives may be excellent
materials for organic electronics.
In summary, simple and efficient synthetic routes for H-PAHs
including H-rubicenes, ABTs, and IDTs were developed with
trisubstituted olefins as critical intermediates. These routes avoid
toxic tin and flammable organolithium reagent or Grignard
reagents. Additionally, ambient reaction conditions and
inexpensive substrates make the synthetic routes cost-appealing.
Significantly, a direct comparison between S- and Se-rubicene
were investigated to show that chalcogen-atom doping greatly
affected the physical properties such as crystal structures, energy
levels, the charge transport mobilities and ISC efficiencies.
Table 3. Optical, electrochemical and charge transport properties.
a
a
b
b
λsol
λfilm
Eox
Ered
μh
Cmpd
(V)
(V)
(cm2/Vs)
(nm)
(nm)
4a
4b
346, 446, 500
347, 450, 501
355, 462, 515
0.69
0.66
-0.96
-0.90
0.2
353, 459, 513
0.0069
b
aAbsorption maxima. Eox is the onset potential corresponding to oxidations,
whereas Ered is the onset potential corresponding to reductions.
According to the golden rule of radiationless process, heavy
atom effect and twist structure of 4b may enhance the intersystem
crossing (ISC) from the lowest singlet state (S1) to the lowest
triplet state (T1). Thus, femtosecond transient absorption (TA)
experiments were performed on 4a and 4b in toluene solution to
Acknowledgements ((optional))
This research was supported by the National Science Foundation
under the Center for Chemical Innovation in Selective C−H
Functionalization (CHE-1700982), the NSFC (21774130,
21905277, 91833305 and 51925306), National Key R&D
Program of China (2018FYA 0305800), the Key Research
Program of Frontier Sciences, CAS (QYZDB-SSW-JSC046), Key
Research Program of the Chinese Academy of Sciences
(XDPB08-2), the Strategic Priority Research Program of Chinese
Academy of Sciences (XDB28000000), the International
Partnership Program of Chinese Academy of Sciences
(211211KYSB20170014) and Fundamental Research Funds for
the Central University.
investigate
excited-state
deactivation
process
upon
photoexcitation. TA spectra for both 4a and 4b can be globally
fitted with a sequential two-component model (Figure S17a and
18a). The former component (black line in Figure 2a and 2c) can
be associated with the instantaneous populated S1, and the latter
one (red line) is ascribed to long-lived T1 state resulting from ISC
process. A sharp difference between 4a and 4b is that the
decaying rate of S1, whose lifetimes are 1.85 ns and 93.9 ps,
respectively (Figure 2b and 2d). This clearly implies the ISC
process is largely accelerated in the heavy-atom-containing 4b
compound. Therefore, 4b exhibited a much higher triplet quantum
yield than 4a (~100% vs 38%), achieving the most efficient
generation of triplet excitons through simple chalcogen atom
tuning.[19] The triplet nature of 4a and 4b were further confirmed
by electron paramagnetic resonance (EPR) measurement
(Figure S19) with strong EPR signals.
Keywords: Synthetic Route 1 • Polycyclic Aromatic
Hydrocarbons 2 • Angular-Benzothiophenes 3 •
Indenothiophenes 4 • Rubicenes 5
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Figure
2.
The
species-associated
difference
spectra
(SADS)
[5]
[6]
and concentrations of transient species as a function of time obtained from
global target analysis for 4a (a, b) and 4b (c, d).
The pyrene-containing ABT (5g) emitted deep blue light at
around 462 nm in a fluorescent quantum yield of 9.4% in the solid
(Figure S3). Additionally, the crystal OFET exhibited a good
charge transport mobility of 0.02 cm2/Vs (Table S4). These
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