Journal of the American Chemical Society
COMMUNICATION
pathways partially overlap. The misaligned three-component
anti-OMARG SHJ 20, in which the position of the red and
unsubstituted NDIs in 18 is switched, was also assembled by
partial stack exchange from 14 to assess the significance of this
novel construct (l ≈ m; Figure 4D and Figure S8C).
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The effect of redox gradients was clearly seen in the depen-
dence of the short-circuit current density JSC on the light
intensity I (Figure 4F). Their relationship is often described by
the equation JSC µ Iα. The exponent α has been shown to be
related to the bimolecular recombination loss efficiency ηBR (the
(5) Sakurai, S.; Areephong, J.; Bertone, L.; Lin, N.-T.; Sakai, N.;
Matile, S. Energy Environ. Sci. 2011, 4, 2409.
fraction of charges lost by recombination) by the equation ηBR
=
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αꢀ1 ꢀ 1.15 As expected, the lowest ηBR was found for the systems
with correctly oriented antiparallel redox gradients in the two
channels (22 ( 3% for 19; b in Figure 4F). The lower ηBR
obtained for 18 (53 ( 8%; 2 in Figure 4F) in comparison with its
constitutional isomer 20 (76 ( 8%; 4 in Figure 4F) is in
agreement with the favorable effect of the gradient in minimizing
charge recombination and supports the occurrence of partial
hydrazone exchange from the surface of the film. On the other
hand, the ηBR obtained for three-component OMARG SHJ 18
was significantly higher than that for four-component OMARG
SHJ 19 and almost the same as that of simple SHJ 14 (50 ( 3%;
O in Figure 4F). These results demonstrate that double-channel
redox gradients are needed to minimize the loss of charges.
Taken together, our results show that stack exchange in SOSIP
architectures can be considered as a unique, reliable, and general
approach for building ordered and oriented multicomponent
systems of appreciable sophistication in a straightforward,
user-friendly manner. Our current objective is to maximize the
complexity accessible by subunit exchange on the one hand and
to explore the potential for practical applications on the other.
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’ ASSOCIATED CONTENT
(14) Chou, C.-M.; Lee, S.-L.; Chen, C.-H.; Biju, A. T.; Wang, H.-W.;
Wu, Y.-L.; Zhang, G.-F.; Yang, K.-W.; Lim, T.-S.; Huang, M.-J.; Tsai,
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S
Supporting Information. Details of experimental proce-
b
dures and additional results. This material is available free of
(15) Koster, L. J. A.; Kemerink, M.; Wienk, M. M.; Maturovꢁa, K.;
Janssen, R. A. J. Adv. Mater. 2011, 23, 1670.
’ AUTHOR INFORMATION
Corresponding Author
Naomi.Sakai@unige.ch; Stefan.Matile@unige.ch
’ ACKNOWLEDGMENT
We thank D. Jeannerat, A. Pinto, and S. Grass for NMR measure-
ments; the Sciences Mass Spectrometry (SMS) Platform for mass
spectrometry services; and the University of Geneva, the European
Research Council (ERC Advanced Investigator), the National Centre
of Competence in Research (NCCR) in Chemical Biology, and the
Swiss NSF for financial support.
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