Journal of the American Chemical Society
COMMUNICATION
onÀoff many times without deterioration (Figure 4E). To probe
the wavelength-dependent response, we utilized band-path filters
for selective excitation of 2D-NiPc-BTDA COFs at different
wavelengths. Interestingly, 2D-NiPc-BTDA COFs were panchro-
matic responsive and exhibited extreme sensitivity to near-infrared
photons (Figure 4F). Photoconductive COFs with vertically
aligned π columns are interesting for the development of organic
electronics. 2D-NiPc-BTDA-COF is unique because it is an
n-channel semiconductor combining broad absorbance up to
1000 nm, panchromatic photoconductivity, and high IR sensitiv-
ity. Such an n-type semiconductor is unprecedented.
In summary, we have developed a strategy for the synthesis of
the first example of n-type semiconducting 2D COFs using
electron-withdrawing blocks. 2D-NiPc-BTDA COFs adopt AA-
type stacking arrangement and exhibit enhanced absorbance over
a wide range of wavelengths up to 1000 nm; they exhibit
panchromatic photoconductivity and are highly sensitive to near-
infrared lights. Owing to the AA-type stacking, 2D-NiPc-BTDA
COFs provide pathways for carrier transport. As a result, the
n-channel 2D-NiPc-BTDA COFs transport electrons with high
carrier mobility. These characteristics clearly originate from the
structural features of the 2D COFs and are hard to achieve with
other n-type semiconductors; thus, this constitutes a new aspect
in the design of π-electronic fucntions of COFs.
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’ ASSOCIATED CONTENT
S
Supporting Information. Complete ref 8, detailed experi-
b
mentalprocedures, FTIRspectra, and simulations. Thismaterialis
’ AUTHOR INFORMATION
Corresponding Author
seki@chem.eng.u-osaka.ac.jp; jiang@ims.ac.jp
Author Contributions
zThese authors contributed equally.
’ ACKNOWLEDGMENT
We are grateful for the financial support of PRESTO, JST. O.S.
thanks the National Research University Project of CHE and the
Ratchadaphiseksomphot Endowment Fund (AM1078I) for fi-
nancial support and a postdoctoral fellowship.
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dx.doi.org/10.1021/ja2052396 |J. Am. Chem. Soc. 2011, 133, 14510–14513