Angewandte Chemie International Edition
10.1002/anie.201904475
COMMUNICATION
channels resemble ideal nanostructured donor-acceptor hole and
electron transporting highways for photocurrent generation.
In conclusion, crystalline, oriented MOF thin films with porphyrinic
("Deutsche Forschungsgemeinschaft"). L.H. acknowledges
funding by the Volkswagen foundation and the DFG (HE7036/5),
and C.W. by the DFG through SPP COORNET. This work was
also supported by the JSPS (KAKENHI Grant Numbers
JP18K14198 (T.H.) and JP18H03898 (H.I.)). The authors thank
Frank Kirschhöfer and Michael Nusser (IFG, KIT) for the help with
the mass spectrometry.
linkers and
C60 embedded in the pores were prepared.
Photoconduction behavior under irradiation with blue light,
exciting the porphyrin Soret band, was found to increase the
electrical conductivity of the SURMOFs by 2 orders of magnitude.
The photoconductance is a result of both, the photosensitive
porphyrin acting as the electron donor and the C60 acting as the
electron acceptor, in addition to the designed MOF structure,
which enables effective electronic coupling within the donor and
acceptor phases. Due to the efficient exciton separation and
transport of the generated electron-hole pairs within the spatially
continuous network of donor and acceptor domains, hole and
electron transport is provided through the close-packed Zn(TPP)
MOF linkers and C60 channels, respectively.
Based on the virtually unlimited possibilities to tune the properties
by appropriate molecular functionalizations of C60 as an electron
acceptor and porphyrin as an electron donor as well as to tune
the absorption properties and absorption wavelength, the MOF
photoconductivity properties can be varied and adopted.
Keywords: photoconduction • metal-organic frameworks •
porphyrin • C60 fullerene • density functional theory
References
[1] a) S. Kaskel, The Chemistry of Metal-Organic Frameworks:
Synthesis, Characterization, and Applications, Wiley, 2016; b) H.
Furukawa, K. E. Cordova, M. O’Keeffe, O. M. Yaghi, Science 2013,
3
41, 1230444.
[
2] a) B. Seoane, J. Coronas, I. Gascon, M. Etxeberria Benavides, O.
Karvan, J. Caro, F. Kapteijn, J. Gascon, Chemical Society Reviews
2
015, 44, 2421-2454; b) H. W. Langmi, J. W. Ren, B. North, M.
Mathe, D. Bessarabov, Electrochimica Acta 2014, 128, 368-392.
[
3] a) C. G. Silva, A. Corma, H. Garcia, Journal of Materials Chemistry
Experimental
2
010, 20, 3141-3156; b) A. A. Talin, A. Centrone, A. C. Ford, M. E.
The porphyrinic SURMOFs and hybrid materials were deposited
on different substrates in a layer-by-layer process using a spin
coater. The samples were characterized by XRD, IR, Raman,
SEM, AFM and UV. Full details of substrates treatment,
preparation and characterization techniques are available in the
supporting information.
Foster, V. Stavila, P. Haney, R. A. Kinney, V. Szalai, F. El Gabaly, H.
P. Yoon, F. Leonard, M. D. Allendorf, Science 2014, 343, 66-69; c)
A. Dragässer, O. Shekhah, O. Zybaylo, C. Shen, M. Buck, C. Wöll, D.
Schlettwein, Chemical Communications 2012, 48, 663-665; d) L. M.
Montanez, K. Müller, L. Heinke, H. J. Osten, Microporous and
Mesoporous Materials 2018, 265 185–188.
[4] P. Z. Moghadam, A. Li, S. B. Wiggin, A. Tao, A. G. P. Maloney, P.
A. Wood, S. C. Ward, D. Fairen-Jimenez, Chemistry of Materials
For measuring the electrical conductivity, the SURMOF samples
were prepared on quartz substrates on which interdigitated gold
electrodes had been deposited. The interdigitated gold electrode
substrates with a total electrode gap length of 3.38 m and a gap
width of 5 µm were obtained from DropSens. Prior SURMOF
synthesis, substrate functionalization was carried out by UV-
ozone treatment for 30 min to remove impurities as well as to
increase the number of surface -OH functional groups. The
conduction of the sample in a pure argon atmosphere was
measured with a Keithley 2635B Sourcemeter. For the current-
voltage curves, the current was measured in 3 cycles and the
arithmetic average value with the standard deviation is shown.
2
017, 29, 2618-2625.
5] A. Morozan, F. Jaouen, Energy & Environmental Science 2012, 5,
269-9290.
[
9
[6] G. D. Wu, J. H. Huang, Y. Zang, J. He, G. Xu, Journal of the American
Chemical Society 2017, 139, 1360-1363.
7] D. Sheberla, J. C. Bachman, J. S. Elias, C. J. Sun, Y. Shao-Horn, M.
Dinca, Nature Materials 2017, 16, 220-224.
8] S. Goswami, D. Ray, K.-i. Otake, C.-W. Kung, S. J. Garibay, T.
Islamoglu, A. Atilgan, Y. Cui, C. J. Cramer, O. K. Farha, Chemical
Science 2018, 9, 4477-4482.
[
[
[
[
9] M. R. Pederson, A. A. Quong, Physical Review B 1992, 46, 13584-
1
3591.
10] G. Yu, J. Gao, J. C. Hummelen, F. Wudl, A. J. Heeger, Science 1995,
70, 1789-1791.
2
More details for the setup can be found in ref.[23b, 30]
.
[11] S. Hamel, V. Timoshevskii, M. Cote, Physical Review Letters 2005,
95.
12] J. Liu, W. Zhou, J. Liu, I. Howard, G. Kilibarda, S. Schlabach, D.
Coupry, M. Addicoat, S. Yoneda, Y. Tsutsui, T. Sakurai, S. Seki, Z.
Wang, P. Lindemann, E. Redel, T. Heine, C. Wöll, Angewandte
Chemie International Edition 2015, 54, 7441-7445.
The light irradiation was performed with LEDs from PrizMatix, with
emission maxima at 365 nm, 400 nm, 455 nm, 530 nm, and
[
-
2
6
1
40 nm, and power densities of approximately 140 mW cm ,
-2
-2
-2
-2
15 mW cm , 127 mW cm , 86 mW cm , and 250 mW cm ,
respectively.
[13] A. Dhakshinamoorthy, A. M. Asiri, H. Garcia, Angewandte Chemie-
International Edition 2016, 55, 5414-5445.
[
14] A. Takai, C. P. Gros, J. M. Barbe, R. Guilard, S. Fukuzumi,
Chemistry-a European Journal 2009, 15, 3110-3122.
[15] L.-L. Li, E. W.-G. Diau, Chemical Society Reviews 2013, 42, 291-304.
Acknowledgements
[
16] a) H. Imahori, T. Umeyama, S. Ito, Accounts of Chemical Research
009, 42, 1809-1818; b) A. D. Schwab, D. E. Smith, B. Bond-Watts,
2
L.X. acknowledges the financial support from Chinese
Scholarship Council (CSC). M.K. is very grateful to F. Symalla and
A. Fediai for fruitful discussions and S. Heidrich for the periodic
calculations. The authors acknowledge funding by M-ERA.NET
MODIGLIANI and SFB 1176. This work was performed on the
computational resource ForHLR II funded by the Ministry of
Science, Research and the Arts Baden-Württemberg and DFG
D. E. Johnston, J. Hone, A. T. Johnson, J. C. de Paula, W. F. Smith,
Nano Letters 2004, 4, 1261-1265; c) M. Muccini, Nature Materials
2006, 5, 605-613.
[
17] a) H. Imahori, Bulletin of the Chemical Society of Japan 2007, 80,
6
21-636; b) D. Kuciauskas, S. Lin, G. R. Seely, A. L. Moore, T. A.
Moore, D. Gust, T. Drovetskaya, C. A. Reed, P. D. W. Boyd, Journal
of Physical Chemistry 1996, 100, 15926-15932; c) M. E. El-Khouly,
C. A. Wijesinghe, V. N. Nesterov, M. E. Zandler, S. Fukuzumi, F.
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