is likely to be the cause for the quenching of the isoalloxazine
emission in the dyad 5. Quenching of the pyrene fluorescence
in 6 seems to be even more effective than in 4. Hence, triad 6
models a structurally confined antenna-charge-separation sys-
tem although pyrene is of minor qualification as antenna.
Nevertheless, the electronic processes in triad 6 appear to be
complicated since both energy transfer and electron transfer
in the excited state regime are competing and are therefore
responsible for the radiationless deactivation. Further studies
using fs-transient absorption and time-resolved Raman spec-
troscopy are underway for clarification. In conclusion, the
model system we presented here fulfills the basic properties
of the light-function of sensory blue light receptors. Studies
are underway in order to optimize the performance specially
with respect to the electrooptical properties of the dye sub-
structures and their structural and geometric architecture.
1H), 4.97 (d, 2H), 6.81 (dd, 1H), 6.99 (m, 2H), 7.11–7.22 (m,
3
H), 7.47–7.51 (m, 2H), 7.66–7.77 (m, 5H), 7.91 (m, 1H), 8.08
m, 1H), 8.14–8.32 (m, 7H), 8.35 (m, 1H), 8.89 (d, 1H) ppm; mass
(
(
+
ESI), m/z: 710.4 (MH ), 1420.8 (2M + H ) (calc. 709.77 for
+
C
44
H
31 5 5
N O ). Compound 5: yellow–orange powder, mp 238–
ꢃ
240 C. IR (KBr): 3908, 3756, 3656, 2932, 1748, 1710, 1655,
1585, 1542, 1517, 1466, 1383, 1280, 1123, 1042, 805, 773 cm . H
ꢂ1 1
H NMR (300 MHz, DMSO-d
6
): d 0.86 (t, 3H), 1.25 (m, 6H), 1.43
m, 2H), 1.74 (m, 2H), 3.28 (s, 3H), 3.94 (m, 2H), 6.89–8.01
m, 14H), 8.24 (dd, 1H) ppm; mass (NI-DCIMS), m/z: 599.5
(
(
(
ꢂ
ꢂ
M ), 1198.5 (2M ) (calc. 599.68 for C63
52 6 5
H N O S. compound
6: [1-pyrenepropanoic acid, a-[[[10-[4-(10-heptyl-10H-phonothia-
zin-3-yl)phenyl]-4,10-dihydro-2,4-dioxobenzo[g]pteridin-3(2H)-yl)-
acetyl]amino] phenylmethyl ester, (aR)], orange powder, mp
262–263 C. IR (KBr): 3056, 2924, 2853, 2601, 1739, 1714, 1656,
ꢃ
1
1
9
614, 1602, 1585, 1573, 1556, 1539, 1484, 1463, 1407, 1392, 1388,
346, 1288, 1265, 1238, 1213, 1184, 1159, 1130, 1108, 1037, 1018,
ꢂ1 1
64, 937, 844, 808, 798, 769, 750, 696 cm . H NMR (400 MHz,
CDCl
.94 (m, 4H), 4.74–4.82 (q, 2H), 5.04 (d, 2H), 5.25 (m, 1H), 6.41
d, 1H), 7.0 (d, 1H), 7.2–7.4 (m, 10H), 7.65–7.72 (m, 6H), 7.9–8.6
3
): d 0.89 (m, 3H), 1.25–1.50 (m, 8H), 1.87 (m, 2H), 3.87–
3
(
(
.
+
m, 12H); mass (FAB), m/z: 1005 (M ) (calc. 1005.22). Anal.
S: C, 75.28; H, 5.21; N, 8.36; O, 7.96; S,
.19. Found: C, 75.47; H, 5.34; N, 8.23%.
Acknowledgements
52 6 5
Calc. for C63H N O
3
The authors thank Mrs G. Garcia for providing several CVs,
Dr T. Clark for help in performing the quantum-chemical cal-
culations and Dr Zhiping Bai, Department of Chemistry,
Nanjing University for calculations for our molecular struc-
tures with the Cerius 2 program. Furthermore, financial
support by Deutsche Forschungsgemeinschaft, Volkswagen-
stiftung and Fonds der Chemischen Industrie is also gratefully
acknowledged. This work is part of Graduate College Sensory
Photoreceptors in Natural and Artificial Systems granted by
Deutsche Forschungsgemeinschaft (GRK 640).
2
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1
acetyl]amino] phenylmethyl ester, (aR)], yellow powder, mp
ꢃ
2
1
85–289 C. IR (KBr): 3908, 3755, 3656, 2930, 1743, 1709, 1657,
ꢂ1 1
551, 1461, 1264, 1187, 1030, 847, 752, 697 cm . H NMR (600
6
MHz, DMSO-d ): d 3.70–3.85 (m, 2H), 4.55 (d, 2H), 4.79 (d,
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3269