ORGANIC

LETTERS

A Novel Redox-Fluorescence Switch 2008

Vol. 10, No. 14
Based on a Triad Containing Ferrocene 3065-3068
and Perylene Diimide Units
Ruili Zhang, Zhongliang Wang, Yishi Wu, Hongbing Fu,* and Jiannian Yao*

Beijing National Laboratory for Molecular Sciences, Key Laboratory of Photochemistry,

Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, PRC, and Graduate
UniVersity of Chinese Academy of Sciences, Beijing, 100049, PRC
hongbing. [email protected]; [email protected]

Received May 7, 2008

ABSTRACT

By taking advantage of the features of ferrocene as a redox-active electron donor unit and perylene diimide as a fluorescence unit, a new
redox fluorescence switch can be constructed on the basis of this triad.

Molecular devices have received considerable attention in molecules whose electronic and optical properties can change
the past decades with the ever-increasing interest for mo- reversibly in response to various environmental stimuli.5
lecular electronics and information storage system, as well Among the various switching materials available, using
as the continuous miniaturization of optoelectronic devices.1 fluorescent components is one of the most attractive owing
As an important component of molecular devices, molecular to its high sensitivity and the easy monitoring of the
switches have been extensively explored due to their potential luminescence signals.6 One general mechanism in fluores-
application as molecular valves,2 molecular memories,3 and cence switches is photoinduced electron transfer (PET)7sin
chemical or biological sensors.4 Molecular switches refer to the off state of the switch, PET either to or from the
fluorophore quenches the fluorescence.
(1) (a) Molecular DeVices and Machines: A Journey into the Nano
World; Balzani, V., Ed.; Wiley-VCH: Winheim, Germany, 2003. (b) Tour, (4) (a) de Silva, A. P.; Gunaratne, H. Q.; Gunnlaugsson, T.; Huxley,
J. M. Acc. Chem. Res. 2000, 33, 791. (c) Balzani, V.; Credi, A.; Raymo, A. J. M.; McCoy, C. P.; Rademacher, J. T.; Rice, T. E. Chem. ReV. 1997,
F. M.; Stoddart, J. F. Angew. Chem., Int. Ed. 2000, 39, 3348. (d) Raymo, 97, 1515. (b) Zang, L.; Liu, R.; Holman, M. W.; Nguyen, K. T.; Adams,
F. M. AdV. Mater. 2002, 14, 401. (e) Magri, D. C.; Brown, G. J.; McClean, D. M. J. Am. Chem. Soc. 2002, 124, 10640.
G. D.; de Silva, A. P. J. Am. Chem. Soc. 2006, 128, 4950. (f) Margulies, (5) Molecular Switches; Feringa, B. L., Ed.; Wiley-VCH: Weinheim,
D.; Melman, G.; Shanzer, A. J. Am. Chem. Soc. 2006, 128, 4865. (g) Gust, Germany, 2001.
D.; Moore, T. A.; Moore, A. L. Chem. Commun. 2006, 1169. (6) (a) Andréasson, J.; Kodis, G.; Terazono, Y.; Liddell, P. A.;
(2) Hernandez, R.; Tseng, H.; Wong, J. W.; Stoddart, J. F.; Zink, J. I. Bandyopadhyay, S.; Mitchell, R. H.; Moore, T. A.; Moore, A. L.; Gust, D.
J. Am. Chem. Soc. 2004, 126, 3370. J. Am. Chem. Soc. 2004, 126, 15926. (b) Piguet, C.; Bernardinelli, G.;
(3) (a) Irie, M. Chem. ReV. 2000, 100, 1683. (b) Raymo, F. M.; Hopfgartner, Chem. ReV. 1997, 97, 2005. (c) Liddell, P. A.; Kodis, G.;
Tomasulo, M. Chem.-Eur. J. 2006, 12, 3186. (c) Jiang, G. Y.; Wang, S.; Moore, A. L.; Moore, T. A.; Gust, D. J. Am. Chem. Soc. 2002, 124, 7668.
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2006, 18, 235. 325.

10.1021/ol801053t CCC: $40.75  2008 American Chemical Society

Published on Web 06/25/2008
 Although fluorescent switches have been extensively
explored,8 fluorescence switches based on a redox reaction
center ferrocene (Fc) are still rare and much less well- Scheme 1. Illustration of a Redox Fluorescence Switch Based
on an Fc-Type Electron Donor
studied.9 Our interest is the possibility to modulate the
emission of fluorophore reversibly by redox reaction of the
Fc group.
Herein, we designed a new fluorescence switch based on
donor-acceptor (D-A) molecules, which incorporated a
redox center Fc because of its excellent reversible redox
properties and high stability.10 More importantly, the electron-
donating abilities of the Fc unit can be reversibly modulated
by the chemical or electrochemical redox reaction. For this
study, perylenetetracarboxylic diimide (PDI) was chosen as excited electron acceptor would result in the fluorescence
the fluorophore and electron acceptor. Besides its high quenching of the PDI, with the D-A molecule showing weak
fluorescence quantum yields which are near unity and its fluorescence. Second, after oxidation, the electron-donating
good photo and thermal stability,11 the following consider- abilities of the Fc unit are reduced, and the PET reaction
ations were taken into account. First, the fluorescence would be arrested, leading to fluorescence enhancement.
spectrum of PDI (500 ∼ 650 nm) is not significantly Third, the reduction of the cation of Fc to neutral Fc would
overlapped with the absorption spectrum of the oxidized result in another fluorescence decrease.
cation radical of the Fc moiety (∼ 460 nm). Otherwise, The synthesis and electrochemical and spectral studies of
intramolecular energy transfer would occur efficiently, and a new triad 1 consisting of one PDI unit and two Fc units
thus the expected fluorescence recovery of Fc•+-PDI would were presented, demonstrating that such new redox fluores-
not be observed.12 Second, the lowest excited singlet state cence switches based on the triad 1 can be constructed.
of the Fc unit is higher in energy than that of the PDI Synthesis of triad 1 is depicted in Scheme 2. Starting from
subunit.13 Thus, the reverse electron transfer from PDI* to compound 3 (Scheme 2), which was prepared by reduction
Fc•+ cannot take place. If such electron transfer occurs, the
fluorescence of the D-A molecules cannot be reversibly
modulated by redox reaction.14
Thus, the working mechanism for such a redox fluores- Scheme 2. Synthesis of Triad 1 and the Chemical Structures of
cence switch is proposed as follows in Scheme 1. First, the Reference Compound 5
photoinduced electron transfer (PET) from the Fc unit to the

(7) Bissell, R. A.; de Silva, A. P.; Gunaratne, H. Q. N.; Lynch, P. L. M.;

Maguire, G. E. M.; McCoy, C. P.; Sandanayake, K. R. A. S. Top. Curr.
Chem. 1993, 168, 223.
(8) (a) Zhang, G.; Zhang, D.; Guo, X.; Zhu, D. Org. Lett. 2004, 6, 1209.
(b) Xiao, X.; Xu, W.; Zhang, D.; Xu, H.; Lu, H.; Zhu, D. J. Mater. Chem.
2005, 15, 2557. (c) Li, H.; Jeppesen, J. O.; Levillain, E.; Becher, J.
Chem. Commun. 2002, 846. (d) Herranz, M. A.; Ramey, J.; Guldi, D. M.
Chem. Commun. 2002, 2968. (e) Loosli, C.; Jia, C.; Liu, S.-X.; Haas, M.;
Dias, M.; Levillain, E.; Neels, A.; Labat, G.; Hauser, A.; Decurtins, S. J.
Org. Chem. 2005, 70, 4988. (f) Yan, P.; Holman, M. W.; Robustelli, P.;
Chowdhury, A.; Ishak, F. I.; Adams, D. M J. Phys. Chem. B 2005, 109,
130.
(9) (a) Martı́nez, R.; Ratera, I.; Tárraga, A.; Molina, P.; Veciana, J. Chem.
Commun. 2006, 3809. (b) Sun, L.; Tian, H. Tetrahedron Lett. 2006, 47,
9227.
(10) Ferrocenes; Togni, A., Hayashi, T., Eds.; Wiley-VCH: Weinheim,
Germany, 1995.
(11) (a) Dotcheva, D.; Klapper, M.; Müllen, K. Macromol. Chem. Phys.
1994, 195, 1905. (b) Quante, H.; Greets, Y.; Müllen, K. Chem. Mater. 1997,
9, 495. (c) Würther, F.; Sautter, A. Org. Biomol. Chem. 2003, 1, 240. (d) of Ferrocenecarboxamide,15 direct condensation of 3 with 4
Würther, F. Chem. Commun. 2004, 1564. in the presence of Zn(OAc)2 led to the novel compound 1
(12) Guo, X.; Zhang, D.; Zhang, H.; Fan, Q.; Xu, W.; Ai, X.; Fan, L.;
Zhu, D. Tetrahedron. 2003, 59, 4843. in an overall yield of 43% after purification with column
(13) (a) Giasson, R.; Lee, E. J.; Zhao, X.; Wrighton, M. S. J. Phys. chromatography.
Chem. 1993, 97, 2596. (b) Lee, S. K.; Zu, Y.; Herrmann, A.; Geerts, Y.;
Müllen, K.; Bard, A. J. J. Am. Chem. Soc. 1999, 121, 3513. The solution phase electrochemical properties of the triad
(14) Farren, C.; Christensen, C. A.; FitzGerald, S.; Bryce, M. R.; Beeby, 1 were investigated by cyclic voltammetry (CV). As shown
A. J. Org. Chem. 2002, 67, 9130.
(15) Li, B.; Bian, Zh.; Hu, R.; Zhao, H. Synthesis of Ferrocene
in Figure 1, only a one-electron reversible oxidation wave
DeriVatiVes; Inner Mongolia University Publisher: Hohhot, 2003; p 152. with E1/2(Ox) ) + 0.12 V (vs Fc/Fc+) was observed in the
(16) Chen, S.; Liu, Y.; Qiu, W.; Sun, X.; Ma, Y.; Zhu, D. Chem. Mater. anodic direction, corresponding to the Fc•+-PDI. As ex-
2005, 17, 2208.
(17) This was calculated with the Rehm-Weller equation: ∆GPET ) pected, the oxidation of the PDI moiety was not observed.
E(ox) - E(red) - E(ex) - e2/εr, with E(ox) ) 0.12 V, E(red) ) -0.96 V, In the cathodic direction, triad 1 showed two reversible
λ(ex) ) 490 nm, and e2/εr ) -0.1 eV. See:(a) Rehm, D.; Weller, A. Isr.
J. Chem. 1970, 8, 259. (b) Grabowski, Z. R.; Dobkowski, J. Pure Appl. reduction waves at E11/2(Red) ) -0.96 V and E21/2(Red) )
Chem. 1983, 55, 245. -1.13 V (vs Fc/Fc+), which were attributed to the successive
3066 Org. Lett., Vol. 10, No. 14, 2008
Figure 1. Cyclovoltammogram of triad 1 in CH2Cl2 (scanning
rate 50 mV/s) with thin-plate of platinum as the working Figure 3. (a) Time profiles of fluorescence lifetime measurement
electrode, platinum wire as the counter electrode, Ag wire as of 5 and triad 1 (3.2 × 10-5 M) in CH2Cl2. (b) Residuals for
the reference electrode (-0.430 V vs Fc/Fc+), and n-Bu4NPF6 biexponential fit of 1. (c) Residuals for single exponential fit of 5.
(0.1 M) as the supporting electrolyte.

exponential function giving a single fluorescence lifetime (τ0

formation of the anion radical Fc-PDI- and the dianion
) 4.77 ns). On the other hand, the decay of triad 1 consisted
Fc-PDI2-, respectively.
of a fast decay component (τ1 ) 0.14 ns, 59%) and slow
The fluorescence spectrum of triad 1 was taken in CH2Cl2 component (τ2 ) 3.66 ns, 41%). From the shorter lifetime
using an excitation at 490 nm, which resulted in the excitation compared with 5, an appreciable increase in the decay rate
of the PDI unit. For comparison, the emission spectrum of of triad 1 was observed. It indicates that there may be
the reference compound 516 was also recorded in Figure 2. electron transfer or energy transfer when Fc was linked to
PDI.
We prefer to attribute the origin of the fluorescence
quenching in triad 1 to the photoinduced electron transfer
between the ferrocene unit and the PDI unit because of the
following facts. First, ∆G for the photoinduced electron
transfer from the Fc to the PDI moiety is estimated to be
-1.35 eV,17 and this negative value of ∆G indicates that
this reaction is thermodynamically favorable. Second, there
is no spectral overlap between the absorption spectrum of
the ferrocene moiety and the fluorescence spectrum of the
PDI unit. Hence, the possibility of energy transfer can be
ruled out. In addition, quenching via aggregation of the PDI
chromophore is excluded because the UV/vis spectra do not
show any signs of aggregation (Figure 2). Accordingly, the
shorter τ1 value (0.14 ns) of triad 1 can be attributed
predominantly to charge separation between the Fc and PDI
Figure 2. Fluorescence (dash line) and UV/vis absorption (solid moieties, while the longer τ2 value (3.66 ns) is similar to
line) spectra of triad 1 and 5 in CH2Cl2 (A ) 0.45). Excitation the intrinsic fluorescence lifetime of the PDI chromophore.18
wavelength was 490 nm.
The fluorescence efficiency of triad 1 was estimated by
measuring the fluorescence quantum yields (ΦF) (see Sup-
porting Information) on the basis of the absorption and
Their fluorescence spectra revealed three emission bands
fluorescence spectra taken in CH2Cl2. The fluorescence of 1
located around 533, 577, and 625 nm, which were indeed
was considerably quenched (ΦF ) 3.9 × 10-3, comparable
the mirror images of the UV/vis absorption spectra, implying
with the value of ΦF,Cal) with respect to that of 5 (ΦF )
that the fluorescence of 1 is due to the PDI unit. It is
0.85).19 This great difference in the quantum yields confirmed
noteworthy that the emission intensity of 1 was dramatically
that PET from the Fc unit to the PDI moiety may quench
reduced compared to that of 5 under the same conditions.
the fluorescence of PDI in triad 1.
The fluorescence decay of compounds 5 and 1 in CH2Cl2
was recorded at 530 nm upon excitation at 490 nm. Time
(18) (a) Luo, H.; Fujitsuka, M.; Araki, Y.; Ito, O.; Padmawar, P.; Chiang,
profiles of fluorescence intensities of both compounds were L. Y. J. Phys. Chem. B 2003, 107, 9312. (b) Würthner, F. Chem. Commun.
shown in Figure 3. In the case of 5, the decay obeyed single 2004, 14, 1564.

Org. Lett., Vol. 10, No. 14, 2008 3067

 To test the possibility of 1 to act as a fluorescence switch,
the chemical oxidation of the Fc unit was performed using
Fe(ClO4)3 as an oxidant. As shown in Figure 4, the emission

Figure 5. Stepwise oxidation and reduction cycles carried out in

CH2Cl2 with triad 1 (3.2 × 10-4 M) by chronoamperometric
analysis, which uses fixed potentials at + 0.17 V (for oxidation)
and - 0.30 V (for reduction) changed every 300 s, following the
Figure 4. Fluorescence spectra of triad 1 (4.3 × 10-5 M) in THF in changes by the evolution of the fluorescence intensity at 533 nm
the presence of different amounts of Fe(ClO4)3. Inset: the fluorescence (λex ) 490 nm).
intensity at 533 nm vs the molar equivalent of Fe(ClO4)3.

cation radical of the Fc unit would be reduced to the neutral

intensity of 1 was enhanced dramatically upon the addition state. So the PET from the Fc subunit to the PDI unit can be
of Fe(ClO4)3 to the solution of triad 1, and the fluorescence modulated off and on sequentially, because of the different
intensity grew with an increasing amount of Fe(ClO4)3. This electron-donating ability of the neutral Fc unit and the Fc
result demonstrates the possibility of establishing a new radical cation. As a result, a new reversible redox-
redox-fluorescence switch based on triad 1, as the FcfFc•+ fluorescence switch can be constructed on the basis of triad
transformation can be operated reversibly. 1 by taking advantage of the peculiar features of the Fc-
Electrochemical oxidation of triad 1 was performed by type donor, i.e., the reversible modulation of the electron-
applying an oxidation potential of + 0.17 V (vs Fc/Fc+) to donating abilities of the Fc unit and the PDI as a fluorescent
the solution of 1 in CH2Cl2 (3.2 × 10-4 M) containing read-out unit.
n-Bu4NPF6 (0.1 M) as the supporting electrolyte. As shown In summary, the synthesis and spectra as well as the
in Figure S2A, the fluorescence intensity of 1 was gradually spectroelectrochemical studies of a new and fast redox-
enhanced with the increasing time of electrochemical oxida- fluorescent molecular switch based on a ferrocene-perylene
tion. After applying the oxidation potential for 300 s, no diimide are presented. Chemical oxidation can lead to the
obvious changes were observed in the emission spectrum. fluorescence enhancement for the solution triad 1. Most
Interestingly, a subsequent application of a reduction potential importantly, the fluorescence intensity of the solution of 1 can
of -0.30 V (vs Fc/Fc+) to the oxidized solution resulted in be reversibly modulated by the electrochemical oxidation and
the decrease of fluorescence, and the initial low fluorescence reduction sequentially. Therefore, a new redox fluorescence
intensity of the solution (before applying an oxidation switch can be established on the basis of triad 1. Such behavior
potential) was almost completely recovered after the reduc- of triad 1 can be attributed to the special spectral and redox
tion potential was applied for 300 s (Figure S2B). Oxidation properties of the Fc and PDI units. The synthesis and investiga-
of triad 1 and its subsequent reduction were carried out for tions of new Fc-type triads with other linking groups between
several cycles without any fatigue, as shown in Figure 5. the donor and acceptor are underway. These new triads might
This fluorescence change can be understood by reference find potential applications in designing molecular devices such
to the cyclic voltammogram of 1 (Figure 1), where the cation as probes and sensors for redox processes.
radical of the Fc unit was generated during the oxidation
since the oxidation potential (+ 0.17 V vs Fc/Fc+) applied Acknowledgment. National Natural Science Foundation
was higher than that of the oxidation potential of the Fc unit of China (Nos. 50221201, 90301010, 50502033), the Chinese
in triad 1. When a reduction potential was explored, the Academy of Sciences, the National Research Fund for
Fundamental Key Project No. 973 (2006CB806200).
(19) The quantum yields of charge separation (ΦCS) and fluorescence
quantum yield (ΦF,Cal) were calculated: ΦCS ) [(1/τ1) - (1/τ0)]/(1/τ1) ) Supporting Information Available: Experimental condi-
0.97 and ΦF,Cal ) 1 - ΦCS ) 0.03. Note that the τ1 value is near to the tions and synthesis and characterization of triad 1. This
limit of our instrument, the actual value might be even shorter. See: (a)
Watanabe, N.; Kihara, N.; Furusho, Y.; Takata, T.; Araki, Y.; Ito, O. Angew. material is available free of charge via the Internet at
Chem., Int. Ed. 2003, 42, 681. (b) Araki, Y.; Luo, H. X.; Nakamura, T.; http://pubs.acs.org.
Fujitsuka, M.; Ito, O.; Kanato, H.; Aso, Y.; Otsubo, T. J. Phys. Chem. A
2004, 108, 10649. OL801053T

3068 Org. Lett., Vol. 10, No. 14, 2008