3582 Ind. Eng. Chem. Res.

2000, 39, 3582-3588

Cation Recognition with Fluorophore Crown Ethers1

Çakıl Erk
Science Faculty, Chemistry Department, Istanbul Technical University, Maslak, 80626 İstanbul, Turkey

The fluoroionophore behavior of various macrocycles with oxygen and nitrogen donors was
reviewed in the present paper, and the cationic recognition of alkali and alkaline-earth metals
involving different photophysical effects depending on the fluoroionophore structures was
summarized. Spectrofluorometry is a very sensitive technique measuring both emission and
excitation intensities of a fluorescent molecule that is influenced by the environment. The cationic
recognition of fluoroionophore crown ethers which possess at least two molecular components
with sites that interact with photons as well as ions is studied. Cations mostly induce the changes
in triplet energy relative to the excited singlet state, S1 f T1, and the ground state, T1 f S0. In
the presence of metal cations, the increased phosphorescence lifetime of luminescent macrocycles,
in general, gave complexation-enhanced quenching fluorescence spectra that reduce the
fluorescence lifetime. However, if the phosphorescence lifetime is reduced, the fluorescence life
is increased and the complexation-enhanced fluorescence spectra would be observed. Optical
responses originating from the different photophysical mechanisms of photoinduced charge
transfer, electronic energy transfer, monomer/excimer equilibrium, and internal charge transfer
were represented. The recent studies on the cation recognition of fluorophore macrocyclic ethers
are exemplified and discussed in the present paper.

1. Introduction structures of acting partners, although the radiative

a. Fluorophore Macrocycles. Macrocycles that
possess ionophore ability have been subject to wide
investigations not only for their synthesis but also for
their numerous technological and analytical applica-
tions since their discovery by Pedersen.2 A large number
of organic syntheses and applications have been re-
ported including solvent extraction and membrane
transport procedures, ion-selective electrodes and re-
lated analytical utilities, and recently chromogenic
functionality of macrocycles via optical spectroscopy. In
this paper, among the several reports, we are only
dealing with the representative results of fluorophore
macrocycles along with the new concepts.3-10 Cationic
recognition studies on fluorophore macrocycles have
increased because of interest in inorganic cationic
chemistry. The interaction mechanism of electropositive
ions with the macrocycle dipoles in a solvent is the main
concept. The collected reports in this work were selected
as evidence for photocationic recognition as we discussed
below.11-17 Namely, the macrocycles of photoionic re-
sponse possess at least two molecular components with
sites that interact with photons as well as ions.18-38
b. Introduction to Spectrofluorometry. There are
numerous techniques to study on the cation-binding
phenomenon. However, spectroscopy has the advan-
tages of fast and relatively simple handling and of
calculation procedures as well as attractive perfor-
mances to analyze the complex mixtures. Spectrofluo-
rometry is a very sensitive and selective technique that
measures both emission and excitation intensities of a
fluorescent molecule which is usually influenced by the
characteristics of the environment and small changes
in the positions of the energetic levels ruling the
quantum yield and fluorescence decay.11-17
The origin of fluorescence is a quite well-known
phenomenon involving relaxation of radiative and non-
radiative decays of excited states. The photophysical
interactions depend on the nature of the fluorescing
10.1021/ie000059e CCC: $19.00 © 2000 American Chemical Society
Published on Web 10/02/2000
fluorescence has time to occur when the nonradiative
relaxation rate is short enough.
The prime practical difficulty of the self-quenching
effect of the increased lumophore concentration is
decided with quantum yield estimation which may limit
the quantitative work.
The electronic states transferred are assigned in
different ways because we use the enumerative system
of S0, S1, S2, ..., Sx or T1, T2, etc., where Sx is the singlet
state and Tx is the triplet state. The fluorescence is
allowed via radiative S1 f S0 transitions, while the
T1 f S0 transition is the radiative phosphorescence
decay.11
c. Fluorescence Pathways of Fluoroionophores.
The interactions between the cation and macrocycle and
the role of the fluorescence structures involved in
cationic recognition are considered in this paper.12-38
Interaction of the oxygen dipoles of the macrocycle with
electropositive ions may form thermodynamically stable
complexes.
Plenty of macrocycles have been synthesized to study
molecular and cationic recognition using different physi-
cal methods.7-10 Fluorescence spectroscopy, although,
recently contributed to analytical methods, which esti-
mates the quality and quantity of cationic recog-
nition.11-17
However, the fluorescence strength depends on the
structure and substituent which plays the primary role
in excited singlet and triplet states. Strong fluorophores,
like anthracene, involve the intersystem crossing pro-
cess in depleting the lowest excited singlet state.18-26
The cation complexes of macrocycles with fluorescent
moieties have received more attention recently, in
particular focusing the excited-state decays.27-38
The pioneering reports of Sousa et al. on different
types of naphthalene crown ethers have outlined the
photophysical interactions related to metal complex
formations.18-20 However, the cationic effect and its
 Ind. Eng. Chem. Res., Vol. 39, No. 10, 2000 3583

quantitation could be estimated by the fluorescence

spectroscopy because the cations mostly induce the
changes in the triplet state energy relative to the excited
singlet state energy, S1 f T1, and the ground state
energy, T1 f S0, although they sometimes cause a heavy
atom effect.
The changes on fluorescence emission properties Figure 1. N-(9-Anthracenylmethyl)aza-18-crown-6.
caused by metal cations which are decided by fluores-
cence, φf, and phosphorescence, φp, quantum yield
measurements are essential. However, the computa-
tions among such photophysical interactions may give
different results.
No difference may sometimes be observed between
fluorescence lifetimes, τf, of free and complexed macro-
cycles. However, in the presence of metal cations, an
increased phosphorescence quantum yield, φp, of a
luminescent macrocycle gives complex formation en-
hanced quenching fluorescence spectra (CEQFS), while
φf is reduced. However, if φp is reduced while φf is
increased, the complexation-enhanced fluorescence spec-
tra (CEFS) is observed. This dichotomous role of naph-
thalene-erived macrocycles was reported by Sousa et Figure 2. Bis(9,10-anthracenophane) macrocycle.
al.18,19 The cationic benzocrowns have shown CEFS in
alcohol as reported by Morita et al.20 and by Wolfbeis.21
Because of their extraordinary fluorescent properties,
the 9,10-anthracene-substituted macrocycles have been
widely investigated for cationic interactions which
depend on the temperature as well as the type of cation
and the solvent.22-26
Introduction of a nitrogen atom into the fluoroiono-
phore macrocycle would cause electron-transfer prop-
erties.27-29 Such molecules were perfectly used for cation
detection. The electron transfer between the receptor
part and the fluorophore which is quenched by a bound
ion is called the photoinduced charge transfer (PET)
effect. This interesting area of cation sensing via PET
has been, in particular, widely preserved by de Silva et
al.22-26 The enhanced internal charge transfer (ICT)
types of excited systems have also been applied for
cation-ligand titrations.29
It has been reported by Morita et al. that the fluor-
escence intensity of dibenzo-18-crown-6 was enhanced
by alkali cations in alcohol.21 The excitation spectra
were quite similar to the absorption spectra of the origin
of the 1(π f π*), T1, state, and the quantum yields
increase with reduced temperature as well as with
cation radii in the complexes.
The fluorescence measurements at different temper-
atures along with viscosity work in cationic solutions
have been explained in terms of increases in fluores-
cence lifetimes due to decreased rates of the nonradia- Figure 3. Excitation spectra of benzo-15-crown-5, in the presence
tive decays of internal conversion. However, the rota- of various NaSCN concentrations from top to bottom at 240 nm.
tional spin diffusion at the S1 state may also be involved. Emission λmax: 308 nm.
On the other hand, the conformation of the complex
structure could sometimes be defined depending on the fluorescence spectra.21-41 The most typical structures
photophysical mechanisms. displaying cation-effective fluorescence spectra are dis-
Comprehensive work of Sousa et al. with the different cussed as follows:
naphthalene crowns showed the complicated computa- a. Anthracene Crowns. The anthracene-derived mac-
tions among the rate of radiative fluorescence, S1 f S0, rocycles like 9-anthracene-linked azamacrocycles were
and phosphorescence, T1 f S0, transitions and the reported by Czarnik et al. with water-stable fluorescence
nonradiative loop of intersystem crossing, S1 f T1, and spectra and cationic color changes.15,16 Several an-
internal conversion, S1 f S0.18-20 thracene derivatives involving the PET mechanism were
inhibited by a complex cation, even in the presence of
2. Results CH2 spacer groups, as was reported by de Silva et al.
(Figure 1).22,23
Several types of macrocycles exhibited interesting The cyclopolyoxa-9,10-anthracenophanes of the double
cation recognition depending on the structure and pseudocavity, as reported by Desvergne et al., have
fluorophore moieties observed from the cation-sensitive showed interesting guest-induced excimer formation of
3584 Ind. Eng. Chem. Res., Vol. 39, No. 10, 2000

Figure 4. Intensity changes of fluorescence emission of dibenzo-20-crown-6 (n ) 0 and m ) 2) on the addition of Na+ and K+ in AN
(excitation λmax: 335 nm).

Figure 5. Ratiometric titration on emission spectra of 2,3-naphtho-18-crown-6 with KSCN and NaClO4 versus intensity changes.

Na+-sensitive fluorescence in acetonitrile (AN) which
were less sensitive in methanol (Figure 2).25
b. Benzo and Naphthalene Crowns. The different
naphthalene-macrocycle structures have been shown
to display alternative photophysical pathways because
of a bound cation including the heavy metal role. The
earliest examples of ion binding via low-temperature
fluorescence spectroscopy have been reported by Sausa
et al., who showed the dichotomous effect of altered T1
levels depending on the structure and the cation.18
Morita et al. have presented the nonradiative and
radiative deactivation rates of dibenzo-18-crown-6 com-
plexes at various temperatures, evidencing that the K+/
benzo-18-crown-6 system is the strongest complex.20
Desvergne et al. have studied paracyclophane macro-
cycles that exhibited the excimer formation depending
on the macrocycle conformation and Na+ complex.26
Erk et al. have studied the synthesis and the steady-
state fluorescence spectra of different aromatic crown
ethers and their cation complexes in acetonitrile.40-53
At room temperature benzocrowns exhibited typical
ionophore behaviors on the cationic fluorescence spectra
in acetonitrile as reported by Erk et al. (Figure 3).44 The
cation-binding studies exhibited good agreements with
the cation radii and the type of counterion as well as
the macrocycle size.43-46
The work of Tuncer and Erk on the synthesis and
cation-binding effect of dibenzo-(3n + 2)-crown-n mac-
rocycles exhibited interesting cationic fluorescence spec-
tral results (Figure 4).50

Figure 6. Cationic effect on the fluorescence emission spectra (CEQFS) of 6,7-coumarino-15-crown-5 (n ) 2, R ) CH3) in AN.
Figure 7. Fluorescence emission of NaSCN complexation of 3-(3-cumaril)benzo-15-crown-5 in AN (n ) 2) (excitation λmax: 337 nm).
Such studies in acetonitrile showed, in particular, the
validity of the fluorescence method to estimate selective
cationic recognition even in the case of weaker cationic
interactions.41-53
The study of Yapar and Erk on 2,3-dioxanaphthalene
crowns has shown their good sensor role for alkali
metals. Ion binding is presented throughout CEQFS,
where the counterions have less effect and the cation
selectivities observed were mostly in accordance with
the macrocycle size (Figure 5).51 However, large dibenzo-
3n-crown-n types of molecules were shown to properly
display such a role.54
c. Coumarin Macrocycles. The coumarin (benzo-
1,2-pyrone) groups of quite stable fluorogenic molecules
which possess too short lifetimes, τf, gave the most
interesting results. The observed broad spectral bands
and short lifetimes indicate the role of nonradiative
transitions from the 1(π f π*) state and intersystem
crossing. ISC accounts for only part of the nonradiative
deactivation of the excitation energy state by the nearby
1(n f π*) state. The nonradiative deactivation competes
with the fluorescence emission of dyes, controlling their
laser properties.
However, the interactions which restrict the electron
flow of the π system would decrease the nonradiative
Ind. Eng. Chem. Res., Vol. 39, No. 10, 2000 3585
deactivation probability. The effective lowest triplet
state of coumarin can be assigned to a 3(π,π*) type.
Therefore, the observed perturbations on the above
state, the vibronic interactions between 3(π,π*) and 3-
(n,π*) states, and the spin-orbit coupling between (n,π*)
and (π,π*) states govern the relative dispositions of the
excitation energy and lifetimes of the excited states.32,36-38
The preparation and molecular recognition of the
coumarin-diazamacrocycles were reported by Valeur et
al.,27-29 who reported the ratiometric analyses of the
binding role of alkali and alkaline-earth cations. Iono-
phore properties are attractive for biochemical interests
such as the intercellular metal probes. Accordingly,
Sammes et al. have reported the synthesis of some
coumarin-based macrocycles which displayed very good
potassium selectivity in water.30,31 However, the strong
solvation may sometimes effect the nonradiative decays
that change the interactions to lose the cation selectiv-
ity.
Erk et al. have reported the serial work on the
synthesis and the cationic recognition of different types
of coumarin-crowns using steady-state fluorescence in
AN (Figure 6).44-46,48-53
Cation-binding investigations were quite satisfactorily
observed in AN. However, cations that are well-solvated
3586 Ind. Eng. Chem. Res., Vol. 39, No. 10, 2000
Figure 8. Effect of NaClO4 and LiClO4 on the emission spectra of 3-phenyl-6,7-coumarin-15-crown-5 at λmax ) 443 nm (excitation λmax
) 385 nm).
Figure 9. UV-vis spectra of 9,10-anthraquinone-1,2-15-crown-5 on addition of different amounts of NaClO4 in AN.
by AN, like Li+, may not be completely free to be
complexed. The computation between Na+ and K+
observed via fluorescence is the question in AN because
six-oxygen-membered macrocycles sometimes show bet-
ter Na+ binding than K+ binding.43,48 The ion-binding
results reported by Erk et al. on the novel crown ethers
showed the specific chromophore effect of the cou-
marins.46 3-Coumarin-attached benzocrowns synthe-
sized very recently displayed an excellent cation sensor
role, as shown on Figure 7.
The recent studies of Erk and Bulut on the synthesis
and photoresponsive binding effect of 3-phenylcoumarin
derivatives of macrocycles have shown the role of
substituent on the electron efficiency on the coumarin
moiety regarding the cation selectivity (Figure 8).52
Cox et al. have reported the synthesis and cation-
binding role of 1,8-dioxy- and 4,5-dioxyxanthone crown
ethers with spectrofluorometry.38 Recently, Erk et al.
prepared the same crowns of 2,3-dioxyxanthone deriva-
tives which showed relatively lower fluorescence quan-
tum yields.53
On the other hand, the UV-vis spectra of 1,2-dioxa-
9,10-anthraquinone (Alizarin) crown ethers exhibited
cation-binding effects. In the presence of alkali and
alkaline perchlorate salts, the absorption of macrocyclic
ethers at 373 nm is shifted to 373 nm (Figure 9).47 On
the other hand, 2,3-dioxa-9,10-anthraquinone crowns
did not display marked cationic fluorescence spectra
because of strong quenching.53 However, the binding
role of such neutral chromoionophore macrocyclic ethers
has been recognized since Pedersen,2 because it was
discussed by Löhr and Vögtle.39
3. Conclusions
The appearance of multicomponent molecular systems
would suggest the different molecular photoionic devices
which employ the ions. In principle, the fluoroionophore
macrocycle select the ions in matching receptor and
incident photons to the fluorophore. Certain stoichio-
metries of binding constants of cationic complexes
estimated from ratiometric analyses displayed the
selective sensor role.45,46 The results just gave binding
effects relative to quantum yields whatever the photo-
physical mechanisms involved. However, the photo-
physical mechanisms might also be investigated via
lifetime measurements near the quantitative measure-
ments in preconditioned systems.26,27 Therefore, the
results are more versatile from the point of view of
practical and engineering use if long-lasting cation-
induced light-detecting systems which also respond in
a large concentration range are developed.

Acknowledgment
In this paper, we are pleased to give the leading
references of the potential laboratories. Ç.E. appreciates
the support of Istanbul Technical University to initiate
the topic on Chromo- and Fluorophore Macrocycles.
TUBITAK and Turkish National Planning Directory,
DPT (Project-126), are acknowledged for their generous
support of the continuing projects of Ç.E.
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