J. Phys. Chem.
A 2009, 113, 14081–14086 14081
Experimentation and Theoretic Calculation of a BODIPY Sensor Based on Photoinduced
Electron Transfer for Ions Detection
Hua Lu,† ShuShu Zhang,‡ HanZhuang Liu,† YanWei Wang,† Zhen Shen,*,† ChunGen Liu,*,‡
and XiaoZeng You*,†
State Key Laboratory of Coordination Chemistry, Nanjing National Laboratory of Microstructures and Institute
of Theoretical and Computational Chemistry, Key Laboratory of Mesoscopic Chemistry of the Ministry of
Education (MOE), School of Chemistry and Chemical Engineering, Nanjing UniVersity, Nanjing 210093, China
ReceiVed: July 30, 2009; ReVised Manuscript ReceiVed: October 22, 2009
A boron-dipyrromethene (BODIPY)-based fluorescence probe with a N,N′-(pyridine-2, 6-diylbis(methylene))-
dianiline substituent (1) has been prepared by condensation of 2,6-pyridinedicarboxaldehyde with 8-(4-amino)-
4,4-difluoro-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene and reduction by NaBH4. The sensing properties
of compound 1 toward various metal ions are investigated via fluorometric titration in methanol, which show
highly selective fluorescent turn-on response in the presence of Hg2+ over the other metal ions, such as Li+,
Na+, K+, Ca2+, Mg2+, Pb2+, Fe2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Ag+, and Mn2+. Computational approach
has been carried out to investigate the mechanism why compound 1 provides different fluorescent signal for
Hg2+ and other ions. Theoretic calculations of the energy levels show that the quenching of the bright green
fluorescence of boradiazaindacene fluorophore is due to the reductive photoinduced electron transfer (PET)
from the aniline subunit to the excited state of BODIPY fluorophore. In metal complexes, the frontier molecular
orbital energy levels changes greatly. Binding Zn2+ or Cd2+ ion leads to significant decreasing of both the
HOMO and LUMO energy levels of the receptor, thus inhibit the reductive PET process, whereas an oxidative
PET from the excited state fluorophore to the receptor occurs, vice versa, which also quenches the fluorescence.
However, for 1-Hg2+ complex, both the reductive and oxidative PETs are prohibited; therefore, strong
fluorescence emission from the fluorophore can be observed experimentally. The agreement of the experimental
results and theoretic calculations suggests that our calculation method can be applicable as guidance for the
design of new chemosensors for other metal ions.
1. Introduction yields (commonly Φf > 0.50) and can be excited at relatively
The design of chemosensors for monitoring biologically and long wavelengths (ca. 500 nm).4b,5 In addition, the BODIPY
environmentally important ions in solution, especially heavy and core has a relatively moderate redox potential, which is a
transition-metal (HTM) ions, is currently of great importance.1 prerequisite when aiming at the construction of fluorescent
Among HTM ions, Hg2+ ions is a highly toxic element and is switches based on electron transfer processes.4a For PET sensors,
widely distributed in air, water, and soil because mercury and the receptor and fluorophore are usually separated by a (short)
mercuric salts are used in many industrial processes and products alkyl spacer, electronically disconnecting the π-electron systems
such as chemical manufacturing or as mining byproducts.2 of receptor and fluorophore. In the unbound state, after excita-
Therefore, it is very important to develop sensitive and selective tion, a fast electron transfer from the receptor to the fluorophore
sensors for Hg2+. Currently, remarkable progress in the design, quenches the fluorescence of the system. When the receptor is
synthesis, and characterization of Hg2+-responsive sensors has bound, the receptor redox potential is perturbed and slows down
been made over the past several years.3 However, mechanistic the PET process, reviving fluorescence emission; this logic
studies and theoretic calculations aimed at providing detailed indication can also be reversed.6 In this work, we evaluate the
explanations of how individual sensor provide different optical computational approach in PET sensor and explain why
feedback for Hg2+ and other ions are often lacking, and such compound 1 provides a different fluorescent signal for Hg2+
research will guide the design of next-generation sensors with and other ions.
improved properties.3a 2. Results and Discussion
Recent efforts in our laboratory have focused on developing
2.1. Syntheses. The procedures for the synthesis of BODIPY
BODIPY fluorescence sensors based on photoinduced electron
derivatives 1-3 are outlined in Scheme 1. Compound 3, 8-(4-
transfer (PET) as a transduction mechanism.4 BODIPY sensors
nitro)-4,4-difluoro-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-in-
combine the advantages of high molar extinction coefficients
dacene, was prepared through TFA-catalyzed condensation of
(usually ε > 80 000 M-1 cm-1) and high fluorescence quantum
2,4-dimethylpyrrole with 4-nitrobenzaldehyde in a one-pot
* Correspondingauthors.E-mail:cgliu@[Link](C.L.);zshen@[Link] reaction.7 The nitro group was subsequently reduced to the
(Z.S.). amino group using Fe-HCl (yield 85%), which is condensed
†
State Key Laboratory of Coordination Chemistry, Nanjing National with 2,6-pyridinedicarboxaldehyde and reduced by NaBH4 to
Laboratory of Microstructures. afford the ideal compound 1 (yield 11%).
‡
Institute of Theoretical and Computational Chemistry, Key Laboratory
of Mesoscopic Chemistry of the Ministry of Education (MOE), School of 2.2. Spectroscopic and Detective Properties of 1. The
Chemistry and Chemical Engineering. absorption and fluorescence spectra of 1 (Figure 1) show the
10.1021/jp907331q 2009 American Chemical Society
Published on Web 12/01/2009
14082 J. Phys. Chem. A, Vol. 113, No. 51, 2009 Lu et al.
SCHEME 1: Synthetic Procedure for BODIPY 1-3
characteristic spectroscopic properties of the BODIPY chro- process is followed by a nonluminescent adiabatic process
mophore with slight stoke shifts. In methanol, a strong S0-S1 returning to the ground state. Besides the famous Marcus
transition with a maximum at 497 nm (ε ) 149 000 M-1 cm-1) theory,10 which may lead to quantitative description of the
and a shoulder at shorter wavelength side is observed.8 The kinetics of electron transfer if the coupling between the initial
fluorescence spectrum of 1 displays an emission band at 513 and final states is well accounted, the PET process may also be
nm with low quantum yield (Φf ) 0.003) upon excitation at rationalized pictorially in terms of simple molecular orbital
483 nm due to the PET process from the aniline moiety to the theory, which was first developed by Weller11 and has become
BODIPY fluorophore.9 a prevalent tool to discuss the fluorescence on-off problem.12
We evaluate the selective properties of 1 toward various metal According to Weller’s approach, after photoinduced electronic
ions (Figure 2). Upon the addition of 20 equiv Hg2+, the excitation from occupied orbitals to unoccupied orbitals, the
intensity of the emission band at 513 nm increases dramatically, corresponding orbitals are left singly occupied. Electron transfer
and 32-fold (Φ/Φ0 ) 43) enhancement is estimated. However, process can then be initiated in two situations, where the
the fluorescence intensity of 1 is almost not influenced by the fluorophore serves either as the electron acceptor or as the
addition of other metal ions (Li+, Na+, K+, Ca2+, Mg2+, Pb2+, electron donor. When the fluorophore serves as the electron
Fe2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Ag+, and Mn2+, respec- acceptor, the HOMO of the fluorophore should be lower than
tively). A very small enhancement by the addition of Al3+ (Φ/ that of the receptor so that an electron on the receptor is capable
Φ0 ) 4.2) is observed. To evaluate the further utility of 1 as an of transferring to the fuorophore and filling in the singly
ion-selective fluorescent sensor for Hg2+, the ion interference occupied HOMO. Contrarily, when the fluorophore serves as
experiment is carried out (Figure 2, right). The fluorescence the electron donor, the LUMO orbital of the fluorophore should
intensity is almost identical to that obtained in the absence of be higher than the LUMO of the receptor, which permits the
interfering metal ions, except that Fe2+ has a little influence, excited electron on the fluorophore to transfer to the unoccupied
but there is still 18-fold enhancement at 513 nm in the presence LUMO of the receptor. Accordingly, the above two PET
of 20 equiv Hg2+; these results suggest that 1 could be processes are addressed as reductive-PET and oxidative-PET,
considered as an effective fluorescent turn-on sensor for Hg2+. respectively.5c It is the alternative roles of donor and acceptor
2.3. Theoretic Calculation. Usually, quenching of the for the excited fluorophore that makes PET very complicated.13
original fluorescent emission will take place when the PET In many cases, the success of the above oversimplified
theoretical approach is owing to the fact that for most chro-
mophores the HOMO-LUMO excitation predominantly con-
tributes to the corresponding excited state, which guarantees
the effectiveness of single electron theories. However, the
BODIPY fluorophore under investigation is slightly different.
It has been commonly accepted that the fluorescence emission
of BODIPY is related to the strongest absorption due to S0 to
S1 excitation. TD-DFT calculation indicates that besides HOMO
to LUMO excitation (0.55 participation in excited-state wave
function) HOMO-1 to LUMO also has considerable contribution
to state S1 (0.23 participation in excited-state wave function).
In this case, our calculation will show that such as in compound
1 the process of electron transfer to BODIPY will be initiated
if only the HOMO of the donor is located above the HOMO-1
orbital of BODIPY, as illustrated in Figure 3.
Many researchers tended to evaluate the energy level of the
Figure 1. Absorption (solid line) and fluorescence (dotted line) spectra corresponding MOs by computing on the separated electron
of 1 in methanol. donor and acceptor, respectively.12a,14 Because the interaction
Calculation of a BODIPY Sensor Based on PET J. Phys. Chem. A, Vol. 113, No. 51, 2009 14083
Figure 2. (Left): Fluorescence responses of 1 (5 µM) in the presence of 20 equiv of various cations (Li+, Mg2+, Na+, Ca2+, Zn2+, Cu2+, Cd2+,
Co2+, K+, Mn2+, Ni2+, Ag+, Al3+, Fe2+, Pb2+, and Hg2+) in CH3OH. (Right): Bars represent the final integrated fluorescence response (Ff) over the
initial integrated emission (Fi). White bars represent the addition of 20 equiv different metal ions. Black bars represent the subsequent addition of
20 equiv Hg2+ to the solution, λex ) 483 nm.
Figure 3. Frontier orbital energy diagrams and electron-transfer paths in 1 (diagram A) and after attachment of Zn2+ ion (diagram B).
between the donor and the acceptor is completely neglected, As has been previously discussed, the electron transfer from
the calculated energy levels as well as molecular orbital aniline group to BODIPY fluorophore to reach the S1 state of
diagrams may not precisely represent the real status of the compound 1 is possible due to the fact that the HOMO of the
electrons on these orbitals. Furthermore, the energy levels may substituent is located above the HOMO-1 of the BODIPY.
seriously rely on the partition scheme, which often makes the Electron transfer takes place during the electrons reorganization
conclusion quite artificial. In our study, calculations will always to its lowest vibrational state on the S1 energy surface, which
be performed on the total system, and we will distinguish the prohibits the electron on the LUMO of BODIPY from going
donor orbitals and acceptor orbitals by simply inspecting the back directly, which could explain the low fluorescence quantum
orbital distribution diagram. Figure 3 shows the possible yield of compound 1. However, when combined with metal ions,
pathways of fluorescence emission and electron transfer pro- the energy levels of the molecular orbitals may change greatly,
cesses. To obtain these orbital energies, we need to optimize which might lead to significant changes in energy sequences of
the ground-state structure. Then, we look into the electron these frontier orbitals.
distribution and pick out the orbitals mainly localized on Let us first look at the mercury ion. Experimental observation
fluorophor part to form the left column; similarly, the right showed that after being combined with this ion, compound 1
column comes from orbitals mainly distributed on the receptor presented a dramatic increase in the intensity of the emission
part. The main advantage of this so-called “one-off calculation” band, which implied that electron transfer process was greatly
is that it overcomes the artificial cut of a whole molecule and suppressed in the complex. Geometry optimizations indicate that
reserves the electron correlation between the donor and acceptor a stable complex was formed, with significant changes of the
parts. Actually, a similar scheme has been adopted by Salman conformation of compound 1, as shown in Figure 4. Rotation
et al.12d of the two aniline groups has been observed, which turns the
14084 J. Phys. Chem. A, Vol. 113, No. 51, 2009 Lu et al.
Figure 4. Geometries of 1 and its Hg2+ complex calculated with DFT method.
Figure 5. Frontier orbital energy diagrams and electron-transfer paths in metal-attached molecules. The attachment of Zn2+ (left column) and Cd2+
(middle column) ions provides an efficient electron transfer path, whereas the attachment of Hg2+ ion does not.
lone-pair electrons on the nitrogen atoms toward bounded Hg2+.
Other metal ions induced similar structure change upon binding
with 1.
It is not surprising that all frontier molecular orbital energy
levels in divalent metal-BODIPY complexes are lower than
the corresponding ones in compound 1. Furthermore, the orbitals
mainly located close to the coordination center dropped down
much further than those localized on the BODIPY segment,
which is far from the coordination center. Similar cases are
witnessed for metal ions Zn2+ and Cd2+, which are illustrated
in Figure 5. The way to obtain these relative frontier orbitals
has been described before. As we can see, the orbitals distributed
on the fluorophore (collected in the left-hand side in Figure 5)
almost reserved their nature, as illustrated in Figure 3, whereas
the receptor’s orbitals (collected in the right-hand side in Figure
5) were affected by the metal ions participation. Consequently,
the energy sequence changed significantly. The HOMO orbital
of the original substituent in compound 1 is decreased to far
below the HOMO-1 orbital of BODIPY, and the reductive-PET
process is prohibited. The oxidative-PET might be favored if Figure 6. Frontier orbital energy diagram and electron-transfer path
the LUMO orbital mainly located on the substituent is decreased in compound 1 after binding Cu2+ ion.
to below the LUMO of the BODIPY segment. Our calculations
indicate that for Zn2+ and Cd2+ the oxidative-PET is very Supporting Information Figure S2 might be due to the small
probable to happen because of the ca. 1 eV energy gap of the energy gap, ca. 0.2 eV, between the LUMOs of the fluorophore
two LUMOs. Very interestingly, as could be seen from Figure and receptor according to our calculation (Supporting Informa-
5, Hg2+ shows a little weaker metal ion effect than Zn2+ and tion, Figure S2).
Cd2+, and the LUMO orbital of the receptor is still higher than The mechanism of the quenching of fluorescence by Cu2+
the LUMO of the fluorophore, and the oxidative-PET process might be very different from that of Zn2+ and Cd2+. As shown
cannot be initiated. That explains the fluorescence enhancement in Figure 6, the open-shell electronic structure Cu2+ ion will
phenomena after the addition of the Hg2+ ion. The weak significantly influence the HOMO of the substituent. Unlike
emission observed in the presence of Al3+ ion shown in Zn2+, Cd2+, and Hg2+, the 3d orbitals of Cu2+ greatly contributed
Calculation of a BODIPY Sensor Based on PET J. Phys. Chem. A, Vol. 113, No. 51, 2009 14085
to the HOMO orbital and raised this orbital up to a much higher EtOAc/petroleum ether). Recrystallization from CHCl3/hexane
level that is between the HOMO and HOMO-1 of the BODIPY yielded crystals (89 mg, yield 85%). 1H NMR (500 MHz,
segment. Therefore, the fluorescence may be quenched by a CDCl3, δ): 7.06 (d, J ) 8 Hz, 2 H), 6.86 (d, J ) 8 Hz, 2H),
reductive-PET. 5.99 (s, 2H), 2.57 (s, 6H), 1.51 (s, 6 H). MS (MALDI-TOF):
m/z 339.19 [M]+, 339.188 [M-F]+ 320.103.
3. Conclusions 4.4. Synthesis of Compound 1. Compound 2 (89 mg, 0.26
mmol), 2,6-pyridinedicarboxaldehyde (17 mg, 0.13 mmol), and
We have developed a highly selective sensor based on
a catalytic amount of acetic acid in MeOH (10 mL) were
BODIPY for Hg2+ and have shown the potential of using
refluxed for 24 h. After cooling to the room temperature, NaBH4
theoretic calculations for providing detailed explanations of how
(23 mg, 0.6 mmol) was slowly added with stirring, and the
compound 1 provides different optical feedback for Hg2+ and
reaction mixture was refluxed for a further period of 12 h and
other ions. In the design of the PET sensor, many factors affect
concentrated at reduced pressure. The crude product was purified
the fluorescence intensity such as electron transfer rate and
by silica-gel flash column chromatography (elution with 40%
fluorescence lifetime; however, the more simplistic approach
EtOAc/petroleum ether). Recrystallization from CH3OH/hexane
of comparing relative energy levels is useful and effective in
yielded red crystals (11 mg, yield 10.9%). Mp > 200 °C. λmax
the design of PET sensors as guidance. For BODIPY, it is
(CH3OH)/nm: 497 nm (ε ) 149 000 M-1cm-1). 1H NMR (400
noticed that the HOMO-1 energy level must be considered in
MHz, CDCl3, δ): 7.72 (m, 1 H), 7.28 (m, 2 H), 7.02 (d, J ) 8.2
the explanation of PET process.
Hz, 4H), 6.78 (d, J ) 8.2 Hz, 4H), 5.96 (s, 4H), 4.58 (s, 4H),
2.54 (s, 12H), 1.48 (s, 12H). MS (MALDI-TOF): m/z 762.366
4. Experimental Section [M-F]+, 734.3 [M-2F]+. HRMS-EI: calcd for C45H45B2F4N7Na
4.1. Materials and Instrumentations. All reagents were [M+Na]+, 804.3756; found [M+Na]+, 804.3751
obtained from commercial suppliers and used without further 4.5. Procedures for Metal Ion Sensing. Stock solutions of
purification unless otherwise indicated. All air and moisture- the metal ions (10 mM) were prepared in deionized water. A
sensitive reactions were carried out under nitrogen atmosphere stock solution of 1 (0.5 mM) was prepared in CH3OH and then
in oven-dried glassware. Dichloromethane was distilled over diluted to 5 µM with CH3OH. In titration experiments, each
calcium hydride. Triethylamine was obtained by simple distil- time, a 2 mL solution of 1 (5 µM) was filled in a quartz optical
lation. NMR spectra were recorded on a Bruker DRX500 cell of 1 cm optical path length, and the Hg2+ stock solution
spectrometer and referenced to the residual proton signals of was added to the quartz optical cell gradually by using a
the solvent. Mass spectra were measured with a Bruker micropipet. Spectral data were recorded immediately after the
Daltonics AutoflexII TM MALDI TOF spectrometer. Lumines- addition. In selectivity experiments, the test samples were
cence spectra were measured on an Aminco Bowman 2 prepared by placing appropriate amounts of metal ion solution
luminescence spectrophotometer. Absorption spectra were mea- into 2 mL of solution of 1 (5 µM). For fluorescence measure-
sured with a Shimadzu UV3100 apparatus. The fluorescence ments, excitation was provided at 483 nm, and emission was
quantum yield was calculated using Rhodamine 6G (Φf ) 0.88 collected from 495 to 600 nm.
in EtOH) as a reference.15 4.6. Computational Details. The ground-state structures of
4.2. Synthesis of 8-(4-Nitro)-4,4-difluoro-1,3,5,7-tetram- BODIPY-based compound 1 and its several metal complexes
ethyl-4-bora-3a,4a-diaza-s-indacene (3). 2,4-Dimethylpyrrole were computed using the density functional theory (DFT)
(380 mg, 4 mmol) and 4-nitrobenzaldehyde (302 mg, 2 mmol) method with the hybrid-generalized gradient approximation (H-
were dissolved in dry CH2Cl2 (100 mL) under nitrogen. One GGA) functional B3LYP. Double valence 3-21g basis set was
drop of trifluoroacetic acid (TFA) was added, and the solution assigned to nonmetal elements (C, H, N, B, and F), which
was stirred for 4 h at ambient temperature in the dark. 2,3- guarantees a reasonable balance of the computational cost and
Dichloro-5,6-dicyanoquinone (DDQ, 442 mg, 2 mmol) was the reliability of the results. For the metal elements under
added, and the mixture was stirred for an additional 20 min. investigation, the effective core potential LanL2DZ basis sets
The reaction mixture was then treated with triethylamine (3 mL) were employed to incorporate the relativistic corrections. The
for 5 min. Boron trifluoride etherate (3.2 mL) was added and absorption properties were predicted by time-dependent (TD-
stirred for another 40 min, and the dark-brown solution was DFT) method. All of the calculations were performed with the
washed with water (2 × 20 mL) and brine (30 mL), dried over Gaussian03 program package.16
anhydrous magnesium sulfate, and concentrated at reduced
pressure. The crude product was purified by silica-gel flash Acknowledgment. We are thankful for the financial support
column chromatography (elution with 10% EtOAc/petroleum from the National Basic Research Program of China (nos.
ether) and recrystallization from CHCl3/hexane to yield 2 as 2006CB806104 and 2007CB925103 to Z.S. and X.Z.Y.), NSFC
red crystals (221 mg, yield 30%). 1H NMR (500 MHz, CDCl3, (nos. 20971066 and 20875043 to Z.S. and 20873058 to C.-G.L.).
δ): 8.4 (d, J ) 3 Hz, 2 H), 7.55 (d, J ) 3 Hz, 2H), 6.03 (s, 2H),
2.58 (s, 6H), 1.37 (s, 6 H). Supporting Information Available: Fluorescence response
4.3. Synthesis of 8-(4-Amino)-4,4-difluoro-1,3,5,7-tetram- of compound 1 in the presence of increasing amount of Hg2+,
ethyl-4-bora-3a,4a-diaza-s-indacene (2). Compound 3 (120 frontier orbital energy diagram and electron-transfer path in
mg, 0.325 mmol) was dissolved in 5 mL of methanol. H2O (2 compound 1 after binding with Al3+, Ag+, and Ni2+, and
1
mL) and Fe powder (300 mg, 5.4 mmol) were added, and the HNMR spectra of compound 1. This material is available free
mixture was heated to reflux. Then, the solution of hydrochloric of charge via the Internet at [Link]
acid in methanol (2 mL, 0.5 mol/L) was added dropwise. The
solution was stirred at reflux for 2 h until TLC monitoring References and Notes
indicated complete consumption of the starting material. The
reaction mixture was cooled to room temperature, filtrated, and (1) (a) Amendola, V.; Fabbrizzi, L.; Licchelli, M.; Mangano, C.;
Pallavicini, P.; Parodi, L.; Poggi, A. Coord. Chem. ReV. 1999, 190-192,
concentrated at reduced pressure. The crude product was purified 649–669. (b) Prodi, L.; Bolletta, F.; Montalti, M.; Zaccheroni, N. Coord.
by silica-gel flash column chromatography (elution with 20% Chem. ReV. 2000, 205, 59–83. (c) Rurack, K. Spectrochimica Acta., Part
14086 J. Phys. Chem. A, Vol. 113, No. 51, 2009 Lu et al.
A 2001, 57, 2161–2195. (d) Que, E. L.; Domaille, D. W.; Chang, C. J. Costela, A.; Garcı̈a-Moreno, I.; Gomez, C.; Sastre, R.; Amat-Guerri, F.;
Chem. ReV. 2008, 108, 1517–1549. (e) Kim, H. N.; Lee, M. H.; Kim, H. J.; Liras, M.; López Arbeloa, F.; Bañuelos Prieto, J.; Lı́pez Arbeloa, I. J. Phys.
Kim, J. S.; Yoon, J. Chem. Soc. ReV. 2008, 37, 1465–1472. Chem. A 2002, 106, 7736–7742. (c) Lı́pez Arbeloa, F.; Bañuelos Prieto, J.;
(2) (a) Descalzo, A. B.; Martı́nez-Máñez, R.; Radeglia, R.; Rurack, Martı́anez, V.; Arbeloa López, T.; Lı́pez Arbeloa, I. ChemPhysChem 2004,
K.; Soto, J. J. Am. Chem. Soc. 2003, 125, 3418–3419. (b) Boening, D. W. 5, 1762–1771.
Chemosphere 2000, 40, 1335–1351. (9) Kollmannsberger, M.; Rurack, K.; Resch-Genger, U.; Daub, J. J.
(3) For a recent review, see: (a) Nolan, E. M.; Lippard, S. J. Chem. Phys. Chem. A 1998, 102, 10211–10220.
ReV. 2008, 108, 3443–3480. For selected examples, see: (b) Choi, S. H.; (10) Marcus, R. A. Angew. Chem., Int. Ed. Engl. 1993, 32, 1111–1121.
Pang, K.; Kim, K.; Churchill, D. G. Inorg. Chem. 2007, 46, 10564–10577. (11) Weller, A. Pure Appl. Chem. 1968, 16, 115.
(c) Yuan, M. J.; Li, Y. L.; Li, J. B.; Li, C. H.; Liu, X. F.; Lv, J.; Xu, J. L.; (12) (a) Bañuelos, J.; Arbeloa, F. L.; Arbeloa, T.; Salleres, S.; Amat-
Liu, H. B; Wang, S.; Zhu, D. B. Org. Lett. 2007, 9, 2313–2316. (d) Yuan, Guerri, F.; Liras, M.; Arbeloa, I. L. J. Phys. Chem. A 2008, 112, 10816–
M.; Zhou, W.; Liu, X.; Zhu, M.; Li, J.; Yin, X.; Zheng, H.; Zuo, Z.; Ouyang, 10822. (b) Fan, L. J.; Zhang, Y.; Murphy, C. B.; Angell, S. E.; Parker,
C.; Liu, H.; Li, Y.; Zhu, D. J. Org. Chem. 2008, 73, 5008–5014. (e) Zhang, M. F. L.; Flynn, B. R.; Jones, W. E. Coord. Chem. ReV. 2009, 253, 410–
X.; Xiao, Y.; Qian, X. Angew. Chem., Int. Ed. 2008, 47, 8025–8029. (f) 422. (c) De Silva, A. P.; Gunaratne, H. Q. N.; Gunnlaugsson, T.; Huxley,
Chen, X.; Nam, S. W.; Jou, M. J.; Kim, Y.; Kim, S. J.; Park, S.; Yoon, J. A. J. M.; McCoy, C. P.; Rademacher, J. T.; Rice, T. E. Chem. ReV. 1997,
Org. Lett. 2008, 10, 5235–5238. (g) Suresh, M; Shrivastav, A; Mishra, S; 97, 1515–1566. (d) Salman, H.; Tal, S.; Chuvilov, Y.; Solovey, O.; Abraham,
Suresh, E; Das, A. Org. Lett. 2008, 10, 3013–3016. (h) Domaille, D. W.; Y.; Kapon, M.; Suwinska, K.; Eichen, Y. Inorg. Chem. 2006, 45, 5315–
Que, E. L; Chang, C. J. Nat. Chem. Biol. 2008, 4, 168–175. (i) Lu, H.; 5320.
Xiong, L. Q.; Liu, H. Z.; Yu, M. X.; Shen, Z.; Li, F. Y.; You, X. Z. Org. (13) Lakowicz, J. R. In Principles of Fluorescence Spectroscopy, 3rd
Biomol. Chem. 2009, 7, 2554–2558. ed.; Springer: New York, 2006; pp 335-336.
(4) (a) Shen, Z.; Roehr, H.; Rurack, K.; Uno, H.; Spieles, M.; Schulz, (14) (a) McCarroll, M. E.; Shi, Y.; Harris, S.; Puli, S.; Kimaru, I.; Xu,
B.; Reck, G.; Ono, N. [Link]. J. 2004, 10, 4853–4871. (b) Yu, Y. H.; R. S.; Wang, L. C.; Dyer, D. J. Phys. Chem. B 2006, 110, 22991–22994.
Descalzo, A. B.; Shen, Z.; Röhr, H.; Liu, Q.; Wang, Y. W.; Spieles, M.; (b) Kennedy, D. P.; Kormos, C. M.; Burdette, S. C. J. Am. Chem. Soc.
Li, Y. Z.; Rurack, K.; You, X. Z. Chem. Asian J. 2006, 1, 176–187. (c) 2009, 131, 8578.
Descalzo, A. B.; Xu, H. J.; Xue, Z. L.; Hoffmann, K.; Shen, Z.; Weller, (15) Olmsted, J. J. Phys. Chem. 1979, 83, 2581–2584.
M. G.; You, X. Z.; Rurack, K. Org. Lett. 2008, 10, 1581–1584. (d) Yu, (16) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb,
Y. H.; Shen, Z.; Xu, H. Y.; Wang, Y. W.; Okujima, T.; Ono, N.; Li, Y. Z.; M. A.; Cheeseman, J. R.; Montgomery, J. A., Jr.; Vreven, T.; Kudin, K. N.;
You, X. Z. J. Mol. Struct. 2007, 827, 130–136. (e) Wang, Y. W.; Li, M.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.;
Shen, Z.; You, X. Z. Chin. J. Inorg. Chem. 2008, 24, 1247–1252. (f) Xu, Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.;
H. Y.; Shen, Z.; Okujima, T.; Ono, N. Chin. J. Inorg. Chem. 2006, 22, Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.;
801–807. Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li,
(5) (a) Baruah, M.; Qin, W.; Flors, C.; Hofkens, J.; Vallée, R. A. L.; X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Bakken, V.; Adamo, C.;
Beljonne, D.; Van der Auweraer, M.; De Borggraeve, W. M.; Boens, N. J. Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.;
Phys. Chem. A 2006, 110, 5998–6009. (b) Ulrich, G.; Ziessel, R.; Harriman, Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.;
A. Angew. Chem., Int. Ed. 2008, 47, 1184–1201. (c) Loudet, A.; Burgess, Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich,
K. Chem. ReV. 2007, 107, 4891–4932. (d) Qin, W.; Baruah, M.; Sliwa, M.; S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.;
Van der Auweraer, M.; De Borggraeve, W. M.; Beljonne, D.; Van Averbeke, Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul. G.; Clifford,
B. V.; Boens, N. J. Phys. Chem. A 2008, 112, 6104–6114. S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.;
(6) Rurack, K.; Resch-Genger, U. Chem. Soc. ReV. 2002, 31, 116– Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng,
127. C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.;
(7) Rurack, K.; Kollmannsberger, M.; Daub, J. Angew. Chem., Int. Ed. Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian 03, revision
2001, 40, 385–387. D.01; Gaussian, Inc.: Wallingford CT, 2004.
(8) (a) Qin, W.; Baruah, M.; Van der Auweraer, M.; Frans, C.; De
Schryver, F. C.; Boens, N. J. Phys. Chem, A 2005, 109, 7371–7384. (b) JP907331Q