TD-DFT Study on the Sensing Mechanism of a Fluorescent

Chemosensor for Fluoride: Excited-State Proton Transfer

GUANG-YUE LI, GUANG-JIU ZHAO, YU-HUI LIU, KE-LI HAN, GUO-ZHONG HE

State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics,
Chinese Academy of Sciences, Dalian 116023, China

Received 6 July 2009; Revised 8 October 2009; Accepted 20 October 2009

DOI 10.1002/jcc.21466
Published online 15 January 2010 in Wiley InterScience (www.interscience.wiley.com).

Abstract: An excited-state proton transfer (ESPT) process, induced by both intermolecular and intramolecular
hydrogen-bonding interactions, is proposed to account for the fluorescence sensing mechanism of a fluoride chemo-
sensor, phenyl-1H-anthra(1,2-d)imidazole-6,11-dione. The time-dependent density functional theory (TD-DFT)
method has been applied to investigate the different electronic states. The present theoretical study of this chemosen-
sor, as well as its anion and fluoride complex, has been conducted with a view to monitoring its structural and pho-
tophysical properties. The proton of the chemosensor can shift to fluoride in the ground state but transfers from the
proton donor (NH group) to a proton acceptor (neighboring carbonyl group) in the first singlet excited state. This
may explain the observed red shifts in the fluorescence spectra in the relevant fluorescent sensing mechanism.
q 2010 Wiley Periodicals, Inc. J Comput Chem 31: 1759–1765, 2010

Key words: fluorescent Chemosensor; Time–Dependent density functional theory; hydrogen bond; sensing mecha-
nism; Excited-State proton transfer

Introduction Sobolewski and Domcke,25–29 the transfer of a proton (PT or

ESPT) along the hydrogen bonds can neutralize the charge sepa-
Fluoride, the smallest and most electronegative anion, has ration in the intramolecular charge transfer (ICT) state, reducing
unique chemical properties. Its recognition and detection are of the energy of these states. Consequently, the hydrogen-bond-
growing interest because it is of relevance in food science, den- induced ICT of this kind of chemosensor can be used to detect
tal care, and the treatment of osteoporosis.1–3 Hence, chemosen- the fluoride anion through optical responses, such as UV/Vis and
sors for fluoride, by which fluoride recognition is converted into fluorescence spectroscopy.
highly sensitive and easily detected signals, have been actively As a common sensing mechanism in chemosensors for fluo-
investigated in recent years.4–23 On account of its simplicity and ride, proton transfer through hydrogen bonding often results in a
high sensitivity, fluorescence detection is becoming of increasing classical Brønsted acid–base-type reaction.23 Several spectro-
importance for sensing anions in supramolecular chemistry.4–15 scopic techniques, such as time-resolved fluorescence spectros-
Different anions can be easily discerned with the naked eye by copy, have been used to study this process,24 but they provide
virtue of the distinct fluorescence wavelengths that they elicit.24 only indirect information about photophysical properties and
Hydrogen-bonding interaction is the most popular and impor- geometries. To further understand the sensing mechanism, we
tant way underpinning chemosensors designed to detect fluoride. could use density functional theory (DFT) and time-dependent
Many neutral chemosensors containing N

H moieties enable density functional theory (TD-DFT) to clarify fundamental
selective anion recognition in aqueous solution. It is noted that a aspects concerning the hydrogen bond formation in the S0 and
p-system bearing an N

H moiety may be an appropriate candi- S1 states, respectively. Previous theoretical studies have revealed
date for designing fluoride chemosensors, because the N

H that a PT or ESPT process is often responsible for the colorimet-
moiety tends to bind the fluoride anion (F–H

N) through
hydrogen bonding.21,22 An sp2-hybridized nitrogen atom in a p-
system is more electronegative than a saturated nitrogen atom.
Additional Supporting Information may be found in the online version of
Therefore, the N

H bond is weakened, which favors proton this article.
transfer (PT) in the ground state or excited-state proton transfer
(ESPT). At the same time, the negative charge on the nitrogen Correspondence to: K.-L. Han; e-mail: [email protected]
atom may be delocalized in the p-orbital, especially a frontier Contract/grant sponsor: NKBRSF; contract/grant numbers: 2007CB815202,
orbital. In recent years, many studies have focused on the 2009CB220010
mechanism of such processes.25–30 According to the research of Contract/grant sponsor: NSFC; contract/grant number: 20833008

q 2010 Wiley Periodicals, Inc.

1760 Li et al. • Vol. 31, No. 8 • Journal of Computational Chemistry

ric and fluorescent signaling of chemosensors. However, in these

studies it was not unequivocally established whether proton
transfer takes place in the ground state or the excited state.21
Meanwhile, we have extensively studied excited-state hydrogen
bonding and its influence on the photophysics and photochemis-
try of many systems.
Molecules bearing intramolecular hydrogen bonds, such as
N    H


O or O    H


O, have already been extensively stud-
ied by both experimental and theoretical approaches.31–36 In
many of these studies, strong arguments in favor of the occur-
rence of ESPT have been presented.31–43 For instance, Smith
et al. studied 1-(acylamino)anthraquinones, which undergo ESPT
upon excitation to their singlet excited states.43 A similar exam-
ple of ESPT was found for 1-hydroxy-substituted Nile Red.35 It
is less flexible because both the proton donor and acceptor (the
hydroxyl group and the nitrogen) are integrated into a conju-
Scheme 1. Atomic labeling of part of heavy atoms of the chemo-
gated system. In these studies, the ESPT process was driven by
sensor phenyl-1H-anthra(1,2-d)imidazole-6,11-dione.
electronic rearrangement in the excited state. The process
decreased the O

H distance and thus facilitated ultrafast proton
transfer which led to conversion from an enol to a keto struc-
ture. was chosen as basis sets throughout,44 which is a proper basis
Recently, Peng et al. reported the novel compound phenyl- set for ionic compound.47 Fine quadrature grids 4 were also
1H-anthra(1,2-d)imidazole-6,11-dione and two derivatives employed.45 No constrains for symmetry, bonds, angles or dihe-
thereof as colorimetric and ratiometric fluorescent chemosensors dral angles were applied in the geometric optimization calcula-
for fluoride.22 Each of these structures contains an N    H

O tions. In addition, a test of solvent effects was performed for
intramolecular hydrogen bond in the ground state. It was postu- photochemical properties. The conductor-like screening model
lated that these derivatives interact with fluoride anion by a (COSMO) solvation model was used to consider the solvent
mechanism involving intramolecular ESPT. The fluorescence effects in acetonitrile (e 5 37.5).46 All the local minima were
and 1H NMR spectra showed that the appropriate charge redis- confirmed by no imaginary mode from vibrational analysis
tribution takes place within the deprotonated species. Further- calculations.
more, the unsubstituted chemosensor proved to be the best sen-
sor for fluoride among these systems. Accordingly, it is impor-
Results and Discussion
tant to understand the detailed sensing mechanism of the
interaction between the chemosensor and anions because of its Optimized Structures in the Ground State
clearly crucial role in determining selectivity.6 In the present
work, we report a theoretical study concerning this chemosensor The ground-state structures of the chemosensor (abbreviated as
(see Scheme 1), which may represent a new candidate for inves- PF for neutral molecule) were obtained using the B3LYP func-
tigating the mechanism of fluoride reorganization. The present tional with TZVP basis set. To evaluate the solvent effect, aceto-
calculation aims to provide a complementary view on the sens- nitrile was used in the calculations according to the COSMO
ing mechanism of this molecule. In particular, we have focused solvation model. The local minima only have real frequencies.
our attention on the mechanism relating to the hydrogen-bonding In the presence of fluoride anion, the fluoride complex and anion
interaction between this chemosensor and fluoride anion in both (deprotonated form) of this chemosensor will appear in solution
the ground state and the excited state. due to the contingent Brønsted acid–base-type reaction. There-
fore, we also studied the neutral form, the complex form (abbre-
viated as CF) and the anionic form (abbreviated as AF) of this
Computational Details chemosensor. SCF energies and atomic coordinates are provided
in the Supporting Information. Some of the most important
All the electronic structure calculations were carried out using structural parameters are shown in Table 1. In PF, the H    O18
the TURBOMOLE program suite.37–46 The geometry optimiza- and N1

H bond lengths, as well as the N1

H    O18 bond
tions (tetramethylsilane and imidazole are also included) for the angle, indicate the formation of a weak intramolecular hydrogen
ground state and the first singlet electronic excited state were bond (N1

H    O18). The N1


H bond in CF, which is drasti-
performed, using density functional theory (DFT) and TD-DFT cally lengthened, is much weaker in the neutral form. The
methods, respectively. Becke’s three–parameter hybrid exchange N1

H    F bond angle is calculated to be 166.88 and thus
functional with Lee-Yang-Parr gradient-corrected correlation approaches 1808. This indicates a stronger hydrogen bond
(B3LYP functional) was used in both the DFT and TD-DFT (N1    H

F). Moreover, the calculated distance between H and
methods.38–42 A test of basis sets was performed for photochem- F in the complex form is 0.99 Å, which is very close to the
ical properties for the chemosensor. As a result, the triple-f length of the HF molecule (0.92 Å).48 It is noted that the CF
valence quality with one set of polarization functions (TZVP) form exhibits almost the same geometric structure as AF. There-

Journal of Computational Chemistry DOI 10.1002/jcc

 Sensing Mechanism of a Fluorescent Chemosensor for Fluoride 1761

Table 1. The Calculated Bond Lengths (Å) and Angles (8) for the Three to fluoride in the ground state. We consider CF to be AF
Forms of the Chemosensor PF by the DFT and TDDFT Methods. bonded to a hydrogen fluoride molecule, which explains why
AF and CF are of similar structure and display similar 1H NMR
PF CF AF spectra. Indeed, it is difficult to distinguish them in the above
spectra.
S0 S1 S0 S1 S0 S1

Bond length: Absorption Spectra and Molecular Orbitals

N1


H 1.01 1.02 1.64 2.58 – –

H
F
– – 0.99 0.98 – – We calculated the absorption spectra of the three molecules
O18

H 2.24 2.06 2.43 1.50 – – using the TDDFT/B3LYP/TZVP method with COSMO solvation
C10

O18 1.23 1.26 1.22 1.26 1.22 1.24 model, and compared them with the experimental data.22 As
C13

O19 1.22 1.23 1.23 1.24 1.23 1.25 shown in Figure 2, all of the calculated spectra were in good
Bond angle: agreement with the experimental results. The UV/Vis spectrum
N1


H

F – – 166.8 109.8 – – of PF with the addition of fluoride anion was found to be a
N1


H

O18 114.3 120.6 91.0 87.2 – – superposition of the respective absorption bands of CF and AF.

H

F

O18 – – 102.2 163.0 – – That is to say, there is an equilibrium between CF and AF in
the ground state. Furthermore, each maximum absorption inten-
sity of low energy is a dominant pp*-type transition from the
fore, the two forms are expected to show similar photophysical highest occupied molecular orbital (HOMO) to the lowest unoc-
and chemical properties in the ground state. Vibrational fre- cupied molecular orbital (LUMO). For PF, our theoretical calcu-
quency analysis showed that the C10¼ ¼O18 stretching band lations predict an intense S0–S1 transition at 399 nm with oscil-
appears at 1719 cm21 in PF. Upon the addition of a fluoride lator strength of 0.218. The addition of fluoride to the chemo-
anion, this C10¼ ¼O18 stretching band is shifted to 1670 cm21. sensor induces a red shift of the S0–S1 transition to 466 nm.
This is because the intramolecular hydrogen bond in the neutral According to the optimized geometries reported above, both PF
form strengthens the C¼ ¼O double bond and fluoride can destroy and CF are planar in their electronic ground states. It indicate
this interaction. As expected, the vibrational modes of AF are that the fluoride-induced charge redistribution rather than any
very similar to those of CF. Furthermore, the N1

H stretching conformational change should be responsible for the S0–S1 bath-
vibration frequency is 3621 cm21 and the vibration is of moder- ochromic shift. Thus, the formation of a hydrogen bond between
ate intensity in the neutral form. However, in CF this band dis- this chemosensor and fluoride anion imparts some ICT character
appears and the F

H stretching band at 2839 cm21 exhibits an to the HOMO2LUMO transition, giving rise to the observed red
extraordinary intensity. It is known that the formation of a shift for the first electronic transition. For AF, the absorption
hydrogen bond can change the vibrational frequencies of both maximum can also be assigned to the transition from S0 to S1
the proton-donating and proton-accepting groups. Usually, the state at 489 nm with oscillator strength of 0.178. Furthermore,
stretching vibration mode is shifted toward lower frequency and the excitation energy of the complex form is very close to that
its intensity increases significantly.49,50 From the calculated of the anionic form.
infrared spectra in Supporting Information Figure S1, the shifted The molecular orbitals have been calculated for all of the
stretching band at 2839 cm21 in CF verifies that a stable hydro- forms of the chemosensor PF. As shown in Figure 3, the
gen bond is established between the N1

H group and the fluo- HOMO is delocalized over the phenyl ring and the neighboring
ride anion. imidazole moiety, while the electron density of the LUMO is
Figure 1 shows the calculated 1H NMR spectra, which pro- completely localized on the anthracene moiety. Thus, the S1
vide further structural information (tetramethylsilane was chosen state corresponding to the HOMO2LUMO transition should
as a standard substance in this calculation). Our calculated have intramolecular charge-transfer (ICT) character. The frontier
results are in agreement with the previous 1H NMR titration orbitals involved in the first electronic transitions are shown in
spectrum.24 For PF, the signal at d 5 11.4 ppm is assigned to Supporting Information Table S3. One can note that the nitrogen
the proton of the N1

H group, which is shifted downfield com- atom of the NH moiety makes little contribution to the HOMO
pared to that of an isolated imidazole molecule (d 5 8.1 ppm). in the neutral form, but this contribution is greatly increased in
In CF, the signal of the N

H proton is shifted downfield to d the complexed and anionic forms. This may be responsible for
5 14.1 ppm. This further confirms the formation of an intramo- the observed decrease in the HOMO2LUMO energy gaps for
lecular hydrogen bond between the N

H group and the neigh- CF and AF (2.85eV and 3.03eV, respectively) in comparison
boring carbonyl group. Furthermore, PF can bind fluoride anion with that for PF (3.20eV). On the other hand, the addition of
through an intermolecular hydrogen bond. In the case of CF or fluoride and deprotonation of the chemosensor will destabilize
AF, most of the signals at d 5 7 to 9 ppm in PF are upfield- both the HOMOs and LUMOs, with the energies of the LUMOs
shifted, which may be due to the increasing charge distribution. being markedly increased. This would rationalize the observed
Moreover, it can also be observed that the 1H NMR spectrum of red shifts of the S1 absorptions corresponding to the HOMO-
AF shows a similar shape to that of CF. LUMO transitions for the complexed and anionic forms com-
It is evident that this chemosensor can bind fluoride anion pared to the neutral form. Moreover, it is directly observed that
through an intermolecular hydrogen bond N1

H    F and shows the electron densities of the LUMOs in the three forms are
a strong tendency to transfer the proton of the imidazole moiety localized on the O18 atom. As a consequence, we estimate that

Journal of Computational Chemistry DOI 10.1002/jcc

1762 Li et al. • Vol. 31, No. 8 • Journal of Computational Chemistry

Figure 3. HOMO and LUMO features of PF as obtained from

DFT/B3LYP/TZVP calculations (Isovalue 5 0.3). (A) HOMO; (B)
LUMO.

local minima only have real frequencies. In the S1 state, all three
geometries retain their planar structures, although the dipole
moments are changed (see the Supporting Information). It con-
firms that S02S1 transitions of them have ICT character. The
Figure 1. Top: Calculated chemical shifts in 1H NMR spectra of bond distance H

F is shorter in PF (0.98 Å), which is very
three forms of the chemosensor at DFT/B3LYP/TZVP level, TMS is close to that in a free HF molecule. As mentioned above, it has
chosen as a standard substance. (A) PF; (B) CF; (C) AF. Bottom:22 been demonstrated that the intramolecular proton transfer can be
Partial 1H NMR (400 MHz) spectra of the chemosensor (1022 M) in facilitated by the hydrogen bonds in the excited state. In particu-
CD3CN in (A) the absence of [(Bu)4N]F; (B) the presence of 10.0 lar, it has further been confirmed that the N

H near the car-
equiv of [(Bu)4N]F. bonyl group often exhibits excited-state proton transfer
(ESPT).38–43 This ESPT process cannot proceed in the chemo-
the O18    H bond length is shortened and the hydrogen bond sensor in the absence of fluoride anion. In CF, relaxation to the
between O18 and H is significantly strengthened after the stable S1 geometry involves proton transfer from a nitrogen do-
HOMO2LUMO transition. nor to an oxygen acceptor. The O18    H bond length is signifi-
cantly shortened to 1.50 Å but the N1    H distance increases to
Optimized Structures in the First Singlet Excited State 2.58 Å compared to the respective bond lengths in the ground
state. Moreover, the F

H    O18 bond angle changes from
We also obtained the excited-state structures of the chemosensor 102.2 to 163.08. The interaction in the fluoride complex is so
at TDDFT/B3LYP/TZVP with COSMO solvation model. The

Figure 4. Comparison of experimental florescence spectra22 and

22
Figure 2. Comparison of experimental UV-Vis spectra and calcu- calculated emission band obtained by TD-DFT/B3LYP/TZVP
lated absorption band obtained at TD-DFT/B3LYP/TZVP level. method. (Green dash) experimental florescence spectra for PF; (Red
(Green dash) experimental UV-Vis spectra for PF; (Red dash) ex- dash) experimental florescence spectra for PF with the addition of
perimental UV-Vis spectra for PF with the addition of [(Bu)4N]F; [(Bu)4N]F; (Blue lines) calculated emission band of PF, CF, and
(Blue lines) calculated absorption band of PF, CF, and AF. AF.

Journal of Computational Chemistry DOI 10.1002/jcc

 Sensing Mechanism of a Fluorescent Chemosensor for Fluoride 1763

Scheme 2. The entire fluorescence sensing processes for the chemosensor phenyl-1H-anthra(1,2-d)im-
idazole-6,11-dione. (A) neutral form; (B) complex form; (C) anionic form.

weak that most characteristics of the excited-state complex form the lower part of Scheme 2. First, the chemosensor binds a
tend towards those of AF with a discrete HF molecule. fluoride ion through an intermolecular hydrogen bond, with con-
comitant proton transfer from N1 to fluoride. Second, the
Emission Spectra
anion2chemosensor complex interacts with its environment and
deprotonation of the chemosensor is induced. Based on a Mul-
As shown in Figure 4, these photophysical characteristics of the liken population analysis of the ground state, we have found
excited states of the three forms are also in good agreement most of the atomic populations in the complexed form to
with the experimental results.22 For all three forms, it is be quite different from those in the neutral form, but close to
observed that, after relaxation of the S1 excited state, the energy those in the anionic form. This confirms that charge distribution
of the first electronic transition decreases significantly. This tran- takes place mainly in the first equilibrium rather than the second
sition should correspond to the respective emission energies. one.
The oscillator strength values of the S12S0 transition in PF, CF The potential-energy curves of CF as a function of the
and AF are 0.204, 0.041 and 0.086 respectively. PF displays a N1

H bond length are studied to understand the proposed
band with a maximum at 546 nm. When fluoride is added, a ESPT process (shown in Fig. 5). The energies of S1 state have
red-shifted emission centered at 677 nm emerges, which can be
assigned to the long-wavelength emission of the ESPT process.
For AF, this band is shifted to 621 nm. It can clearly be
observed that the emission wavelengths of CF are much longer
than the absorption wavelengths. The emission band of AF is
red-shifted by about 75 nm in comparison with that of the neu-
tral form according to our TDDFT calculation. The Stokes shift
of the complex form is larger than that of the other two forms,
since the change in charge distribution of the complex form after
the proton transfer is more pronounced.

Equilibria and Sensing Mechanism

It has been reported that formation of the intermolecular hydro-

gen bond has little disruptive influence on the dipole associated
with the charge-transfer transition of this chemosensor, and con-
sequently, only a small spectral change is observed.22 However, Figure 5. Potential-energy curves of CF of S0 (black squares), and
the theoretical results suggest the opposite to be the case. As S1 (red circles) states, calculated at the TD-DFT/B3LYP/TZVP level
mentioned above, the interaction between this chemosensor and as functions of the N1

H bond length in the S1 state (ESPT coordi-
the sensed fluoride is indeed based on two chemical equilibria in nate). The energies of S0 state have been calculated at the optimized
the ground state. These equilibria can be depicted as shown in geometries of the S1 state.

Journal of Computational Chemistry DOI 10.1002/jcc

1764 Li et al. • Vol. 31, No. 8 • Journal of Computational Chemistry

been optimized for the N1

H bond length, while the energies between its N

H group and the neighboring carbonyl group in
of S0 state have been calculated for the optimized geometries of its ground state. Addition of fluoride anion at this N

H group
the S1 state. The energy of S1 state decreases along the ESPT induces the formation of a new hydrogen bond with concomitant
process coordinate with no barrier. It is clear that the nature of capture of the proton. After excitation, the HF moiety in the
emitting state after addition of fluoride anion is different from complex form shifts to the neighboring carbonyl group to form
that of absorbing state. CF, which can be regarded as AF bind- another hydrogen bond through an anion-induced ESPT process.
ing a HF molecule at the position of N1, spontaneously presents Emission transition energies are relatively well reproduced by
the transfer of proton from N1 to carbonyl by the excitation of TD-DFT vertical transition energies computed from the first sin-
light. Then, fluorescence of CF released from the excited states. glet excited optimized geometries. The relaxation of the excited
In this case, CF can be regarded as AF binding a HF molecule states induces a significant lowering of their first electronic tran-
at the position of carbonyl. The results successfully interpret the sitions, which makes the fluorescent difference between this che-
previous conclusion that ESPT process can proceed spontane- mosensor and its fluoride complex. The fluorescence sensing
ously in the S1 state. mechanism for fluoride anion has been verified to be in accord-
Considering the two equilibria in the ground state and the ance with the reported results. The tautomeric structure of the
potential-energy curves mentioned above, we can delineate the fluoride-chemosensor complex makes a major contribution to the
fluorescent sensing mechanism of this chemosensor as follows: dissociation of the HF molecule in the excited state. In conclu-
In the excited state, the fluoride anion can capture the proton of sion, the overall mechanism is based on a hydrogen-bonded
the NH group to form an intramolecular hydrogen bond. Subse- excited-state complex and an anion-induced ESPT process.
quently, ESPT takes place in this chemosensor, with NH acting
as a proton donor and the neighboring carbonyl group acting as
a proton acceptor (However, we are supposing the lifetime of References
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Journal of Computational Chemistry DOI 10.1002/jcc