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Inorganica Chimica Acta 293 (1999) 53 – 60

Thermodynamic and structural study of inclusion complexes

between trivalent lanthanide ions and native cyclodextrins
Nicolas Fatin-Rouge, Jean-Claude G. Bünzli *
Uni6ersité de Lausanne, Institut de Chimie Minérale et Analytique, Unité de Recherche sur les Eléments f, BCH 1402,
CH-1015 Lausanne, Switzerland

Received 12 February 1999; accepted 4 May 1999

Abstract

The interaction of trivalent lanthanide ions (Ln3 + ) with native cyclodextrins (CDs) is investigated in acidic and basic aqueous
media. At low pH, the association constants for 1:1 complexes are in the range log K =2–4 (m= 0.1 M, NaCl or TMACl), as
determined by pH-potentiometric study of the hydrolysis of the Ln ions in absence and in presence of CDs. The thermodynamic
parameters of the inclusion reaction show that the complexation of Ln3 + ions inside the CD cavity is entropically driven and does
not depend upon the host. 1H and 13C NMR spectra point to inclusion of La3 + cations in the cavity of a-CD occurring in the
narrowest part of the host molecule, close to the C5 carbon atoms. a-CD acts like a crown ether, its anomeric oxygen atoms being
the donor atoms. Complexation of Tb3 + by partially deprotonated a-CD was investigated at pH 12.33: 13C NMR measurements
show that complexation occurs at the OH-3 secondary hydroxyl groups of a-CD while UV – Vis spectrophotometric titration leads
to an apparent constant log Kapp :4.2 (1:1 complex). Lifetime measurements of the Eu(5D0) and Tb(5D4) levels confirm these
findings. © 1999 Elsevier Science S.A. All rights reserved.

Keywords: Cyclodextrin complexes; Thermodynamics; Lanthanide complexes

1. Introduction complexation remains a challenge for synthetic

The search for efficient luminescent sensors and
switches for the analysis of biomaterials is presently
stimulating a wealth of interest [1,2]. In this context,
both trivalent lanthanide ions (Ln3 + ) and cyclodextrins
(CDs) hold a distinctive place, because the first have
luminescent properties that are environment sensitive
[3] and the second provide specific and protective mi-
cro-environments for small molecules included in their
cavity [4,5]. Lanthanide-centered luminescence is easy
to sensitize by the antenna effect [6], but avoiding
de-activation through high energy vibrations of bound
ligands or of solvent molecules is more difficult [3].
Indeed, small water molecules interact strongly with
Ln3 + ions and the design of a coordination environ-
ment bearing chromophores suitable for an efficient
antenna effect and protecting the LnIII ions from water
* Corresponding author. Tel.: + 41-21-692 3821/3850; fax: +41-
21-692 3825.
E-mail address: jean-claude.bunzli@icma.unil.ch (J.-C.G. Bünzli)
chemists.
CDs have moderate solubility in water and are
known to include organic molecules or fragments in
their cavity. This property can be used to generate close
contacts between these fragments and complexed
cations, as demonstrated with modified CDs [7,8]. In
this respect, the recent elaboration of rules for selective
substitutions at the hydroxyl positions of CDs [9] led to
the design of efficient supramolecular devices and archi-
tectures [5,10,11]. CDs can also include coordination
complexes [12] with sizable binding constants as large
as 2000 M − 1 [13]. They are expected to reduce deacti-
vation of luminescent excited states of LnIII ions and to
enhance the luminescence intensity of chromophores
[14,15] and/or the yield of the energy transfer onto the
Ln3 + ion [8].
For these reasons, we have launched a research pro-
gram aiming at investigating second sphere Ln3 + com-
plexation by CDs and its effect on the photophysical
properties of the lanthanide ions. In absence of funda-

0020-1693/99/$ - see front matter © 1999 Elsevier Science S.A. All rights reserved.
PII: S 0 0 2 0 - 1 6 9 3 ( 9 9 ) 0 0 2 2 7 - 3
54 N. Fatin-Rouge, J.-C.G. Bünzli / Inorganica Chimica Acta 293 (1999) 53–60
mental data on Ln3 + – CDs interaction, but for one
partial study on the dissolution of praseodymium hy-
droxide by a- and g-CDs in basic medium [16], we have
started our study by looking at inclusion complexes of
Ln3 + aqua-ions with native CDs. In this paper, we
report thermodynamic and structural data on the inser-
tion of La3 + (aq) in a-, b-, and g-CD and of Ln3 + (aq)
in a-CD in acidic solutions, as well as of the association
of Tb3 + (aq) with a-CD at basic pHs.
2. Experimental
2.1. Sol6ents and stating materials
All the chemicals used in this study were of analytical
grade and were used without further purification: a-, b-
and g-CDs, tetramethylammonium chloride (TMACl),
tetramethylammonium hydroxide (TMAOH) (Fluka),
NaCl, Na2B4O7, Na2CO3, NaHCO3 (Merck). Stock so-
lutions of Ln(ClO4)3 ( 8 mmol l − 1) were prepared
from lanthanides oxides (99.99%, Rhône Poulenc).
Ln3 + solutions were prepared just before use from
freshly boiled doubly distilled water saturated with N2.
They were acidified systematically with HCl to pH 4
before complexometric titration, to avoid hydroxide
precipitation; standardized Na2H2EDTA solution in
urotropine buffered medium was used along with
xylene orange as indicator. Stock solutions of CDs
( 8 mmol l − 1) were prepared from freshly boiled
doubly distilled water saturated with N2. The concen-
trations of CDs were calculated from the optical rota-
tion of sodium light at 25.0°C (a-CD =150.5 9 0.5°,
b-CD =162.590.5° and g-CD = 177.5 9 0.5° [17]).
Substances used for 1H NMR were dried under vacuum
after dissolution in D2O.
2.2. pH Potentiometry
The hydrolysis constants of Ln3 + and the association
constants with non deprotonated CDs were determined
by pH potentiometric titrations of 0.002 M metal solu-
tions in absence and in presence of 1 equiv. of CD [18].
Care was exercised to analyze the pH domain in which
CDs are non deprotonated. The titrations were carried
out using 20 ml sample solutions in a thermostated
(25.0 9 0.1°C) glass-jacketed vessel under Ar atmo-
sphere. The ionic strength of the solutions was held
constant (m =0.1 M) by adding an aliquot of NaCl or
TMACl. Reactants were mixed in the thermostated
vessel and acidified to pH 4.0090.02 (HCl) at least 30
min before titration. Titrations were carried out with an
automatic Metrohm Titrino 736 GP potentiometer (res-
olution 0.1 mV, accuracy 0.2 mV) using a constant
volume addition (0.1 ml) program and linked to an
IBM PS/2 computer. An automatic burette (Metrohm
6.3013.210, 10 ml, accuracy 0.03 ml), was used along
with a Metrohm 6.0238.000 glass electrode. The latter
was prepared with the same electrolyte and at the same
ionic strength (0.1 M) than the solutions to study in
order to minimize junction potentials; traces of silver
nitrate were added and after measurement the electrode
was left in an acidic solution (HCl, pH 2.5); the elec-
trode was used 48 h after conditioning. The following
Metrohm buffer solutions were used to calibrate the
electrode: 62305.010 (pH 4.00), 62305.020 (pH 7.00),
62305.020 (pH 9.00), and 0.025 M Na2CO3-NaHCO3
(m=0.1 M, NaCl or TMACl; pH 10.01 [19]). The data
(60 points per curve, drift 1 mV mn) were treated
mathematically by the program SUPERQUAD [20]
using a Marquardt algorithm. The following values of
the ionic product of water were taken into account
(m= 0.1 M): pKw = 13.72 (NaCl [21]) and pKw =13.93
(TMACl), as determined from HCl–TMAOH titration.
2.3. Spectrophotometric titrations
Electronic spectra were recorded with a Perkin–
Elmer l-900 spectrophotometer at 25.0°C (205–500
nm, 100 nm min − 1 scan-speed) using 0.1 cm quartz
cells. Titration of a 0.009 M a-CD solution (20 ml) by
Tb(ClO4)3·nH2O (0.467 M, pH 4) was performed at pH
12.3090.05 in a thermostated (25.09 0.1°C) glass
jacketed vessel and under Ar atmosphere. The pH was
maintained constant during the titration by addition of
KOH 0.5 M. The Ln3 + solution was added with fast
mixing to avoid local excess and precipitation. Under
these conditions, equilibrium was attained within 10
min. The [Tb3 + ]/[a-CD] ratio ranged from 0 to 1.3. A
15 min time delay was imposed after each 20.0 ml
addition, before 0.3 ml of solution was transferred into
a quartz cell with a Teflon® syringe. The apparent
complexation constant was determined using the SPEC-
FIT program [22].
2.4. NMR measurements
1
H and 13C spectra were collected on DPX-400 or
AM-360 Bruker spectrometers. 1H NMR spectra were
recorded in D2O and 13C spectra were recorded in
H2O/D2O 50/50 v/v using methanol as external refer-
ence. Assignment of the 13C spectra was done using 1H
decoupling, DEPT (distortionless enhancement by po-
larization transfer) 135 [23] and previously published
results [24]. 1H NMR spectrum of a-CD was assigned
following Woods et al. results [25]. Chemical shifts of
a-CDs H2-6 protons were obtained using selective irra-
diation. The a-CD titration with La3 + (aq) in acidic
solution was monitored by 13C NMR as follows: five
samples of a-CD  0.05 M (0.107 g, 2 ml) were pre-
pared and La(ClO4)3·nH2O was added to yield [La3 + ]t /
[a-CD]t ratios ranging between 0 and 2. Both the LaIII
 N. Fatin-Rouge, J.-C.G. Bünzli / Inorganica Chimica Acta 293 (1999) 53–60 55

salt and the a-CD were titrated just before measure-
ment to determine their exact hydration number. The
pH was adjusted to 4.5 using 1 to 7 ml of H2SO4(aq)
and a glass electrode.
For titration in basic medium, Tb(ClO4)3·nH2O 0.467
M in H2O was added to a solution of a-CD (7.2 ml,
0.15 M in H2O/D2O 50/50 v/v, pH 12.33 90.03) ther-
mostated at 25.090.1°C in a glass jacketed vessel
under Ar atmosphere. The pH and the solvent compo-
sition were adjusted and 0.5 ml were syringed from the
titration vessel for analysis. pH values were measured
using a calibrated glass electrode in H2O/D2O 50/50 v/v
with KOH solution. A slight turbidity appeared for
[Tb3 + ]t /[a-CD]t \ 1.09, which increased with further
metal addition and these were filtered before analysis.
2.5. Lifetime determination
Eu(5D0) and Tb(5D4) lifetimes were measured on
solutions 0.025–0.1 M in both bidistilled and degassed
water and deuterated water. Selective pulsed excitations
were achieved with a tunable dye laser (Lambda Physik
FL-3002) pumped with a XeCl excimer laser (Lambda
Physik EMG 101 MSC, pulse width: 18 ns). Rho-
damine 6G was used for Eu which was excited though
the 5D0 ’ 7F0 (578.5 nm) or 5D0 ’ 7F1 transition (588
nm) while coumarine 102 was used to excite Tb through
its 5D4 ’ 7F6 transition at 488 nm. The signal was
averaged with a SR-430 multichannel scaler coupled to
a SR-400 gated photon counter from Stanford Re-
search Systems. Decay curves were treated mathemati-
cally on an IBM PS/2-80 computer using a home made
algorithm. Data are averages of 3 – 5 determinations.
means that CDs do not exchange protons in the pH
range analyzed. Therefore, a special model was adopted
for La3 + , taking into account partially deprotonated
a-CDs. Below pH 10, speciation diagrams show that in
the worst case (i.e. g-CD) monodeprotonated CD ac-
counts for less than 5% and no complex between this
species and La3 + ions was detected. Examination of
Fig. 1 shows that titration curves for La3 + display
some difference between a-CD on one hand and b- and
g-CDs on the other hand. The association constants
with the three CDs are in the range log K=3.8–4
(Table 1) and appear to be almost independent of the
nature of the receptor despite variations in diameter
[29] and polarity [30] of the cavity. Enthalpy (DH) and
entropy (DS) changes were estimated from the tempera-
ture dependence of K in a limited temperature range
(298.2–310.5 K). For a-CD, DH =28.591.8 kJ mol − 1
and DS =1699 6 J K − 1 mol − 1 while these values
amount to 299 4 kJ mol − 1 and 169 916 J K − 1
mol − 1, respectively, for both b- and g-CDs. These

3. Results and discussion

3.1. Insertion of Ln 3 + ions in CDs at acidic pHs

The constants for the association of Ln3 + ions and

CDs were determined from potentiometric titrations of
metal ion solutions in absence and in presence of CDs.
A chloride salt was chosen as electrolyte because this
anion has the smallest association constant with CDs
(for a-CD, 1.5 M − 1 versus 30 – 50 M − 1 for ClO4− [26]).
The pH-potentiometric titration of Ln3 + ions alone
gave accurate values of the acidic hydrolysis constants,
very close to the literature values [27]. Analysis of the
pH titration curves obtained in presence of one equiva-
lent of CD was made introducing an association con-
stant [28] between the Ln3 + cation and CDs:
K = [Ln3 + ·CD]/[Ln3 + ]·[CD]. This model fitted conve-
Fig. 1. Potentiometric titration curves of La3 + (top) and Lu3 +
niently the titration curves and except for La3 + (aq), the
(bottom) ions in absence (1) and in presence of a-CD (2), b-CD (3),
pKa value of which is especially large, addition of CD g-CD (4). [Ln3 + ]0 =[CD]0 =0.002 M, V0 =20 ml, [TMAOH]tit =
to the solutions did not influence the number of base 0.034 M, m= 0.1 M (TMACl), T=25.0 90.1°C (the starting pH
equivalents needed to titrate the Ln3 + ions, which value was reached by adding acid before titration).
56 N. Fatin-Rouge, J.-C.G. Bünzli / Inorganica Chimica Acta 293 (1999) 53–60

Table 1
Association constants (Log K 92s) and thermodynamic parameters
( 9 2s) for the interaction of La3+ with a-, b-, and g-CDs (H2O,
m= 0.1 M TMACl)

T (K) a-CD b-CD g-CD

298.0 3.859 0.12 3.779 0.14 3.77 9 0.14

302.0 3.919 0.10 3.82 90.12 3.82 9 0.12
310.5 4.059 0.10 3.97 90.12 3.97 9 0.12
DH (kJ mol−1) 28.5 91.8 2994 29 9 4
DS (J K−1 mol−1) 1699 6 1699 16 169 9 16

Fig. 2. Association constants of Ln3 + cations with a-CD as deter-

thermodynamic parameters are indicative of an entropi-
cally driven association. Large and positive values for
DH point to a weak metal – ligand interaction energy as
expected for complexation by neutral donor atoms. For
Lu3 + , titration curves with the three CDs are superim-
posable, leading to identical values of log K. In view of
the low dependence of K(Ln3 + ) upon the host, associa-
tion constants for the entire Ln3 + series were deter-
mined with a-CD only (Table 2). A plot of these
constants versus the inverse ionic radii for coordination
number 9 (Fig. 2) displays variations along the lan-
thanide series which are reminiscent of a tetrade effect
[31] and which point to the influence of solvation and
coordination number change on the association pro-
cess. Except for La3 + , for which K is the largest, the
association constants are slightly larger when TMACl is
used as inert electrolyte instead of NaCl, which reflects
some competition between Ln3 + and Na + .
To determine whether the Ln3 + – CD association oc-
curs on the outside or inside the host cavity, we have
recorded 1H and 13C NMR spectra at pH 4.5 in D2O as
a function of R =[La3 + ]tot/[a-CD]tot (Fig. 3). For R=
Table 2
Hydrolysis constants (log b*1–3) a of Ln3+ ions and association con-
stants (log Kass) with a-CD (H2O, T= 25.09 0.1°C); 92s indicated
within parentheses
Ln m = 0.1 M (NaCl) m =0.1 M (TMACl)
mined by competitive potentiometric titrations at 25.0 90.1°C, m =
0.1 M (NaCl), vs. the reciprocal of the ionic radii for a coordination
number of 9 [3].
5, the following chemical shift differences were ob-
served: − 0.016, − 0.020, + 0.040, + 0.014, +0.105,
− 0.011, and + 0.009 for H1, H2, H3, H4, H5, H6a and
H6b, respectively (see Scheme 1). The largest variations
occur for the internal protons H3 and H5 and similarly
to what was observed for aromatic guest inclusion [32],
these protons are de-shielded upon addition of
La3 + (aq). The external protons H2 and H4 sustain
small shifts only and we can reasonably infer that the
metal ion is located near the H5 protons, which are
localized in the narrow part of the conically shaped
CD. To confirm this assignment, we have examined the
13
C NMR spectra and indeed, they show that carbon
atoms C5 have the largest chemical shift variation and
become shielded (Fig. 4). These data are consistent with
steric polarization [33], the H5 and C5 chemical shifts
varying in opposite direction upon metal addition.
Moreover, the resulting shortening of the C5 –H5 bond
is confirmed by the large variation of the coupling
constant 1JCH with added metal ion (Table 3). To
explain these data more quantitatively, we apply the
theory of steric polarization of C–H bonds by a proton
H% to the system C5 –H5 –La3 + (Scheme 1). The 13C
chemical shift (dC13) is a function of the angle C–H–La
(u) and of the H–La distance (r) [33]:

log b*
1–3 log K log b*1–3 log K

La −26.12 (5) 3.98 (4) −26.41 (5) 3.85 (6)

Pr −24.00 (4) 2.91 (8) −24.28 (4) 3.25 (8)
Nd −23.54 (4) 2.8 (1) −23.88 (5) 3.40 (7)
Sm −22.34 (4) 2.7 (1) −22.78 (5) 3.18 (7)
Eu −22.21 (5) 2.6 (1) −22.74 (5) 2.79 (9)
Gd −22.16 (5) 2.5 (1) −22.76 (5) 2.78 (9)
Tb −21.61 (4) 2.78 (9) −22.32 (5) 3.20 (9)
Dy −21.45 (4) 3.23 (9) −22.14 (5) 3.77 (8)
Ho −21.46 (6) 3.66 (8) −22.08 (4) 3.74 (9)
Er −21.33 (5) 3.46 (9) −22.11 (5) 3.6 (1)
Tm −20.86 (8) 2.65 (9) −21.97 (6) 3.0 (1)
Yb −20.68 (6) 2.44 (9) −21.72 (7) 3.0 (1)
Lu −20.71 (6) 2.3 (1) −21.04 (8) 3.0 (2)
Fig. 3. Part of 1H NMR spectra of a-CD alone in D2O (a) and in
a
b* + 3
1–3 =[Ln(OH)3]·[H3O ] /[Ln
3+
]. presence of 5 equiv. of La3 + (b) at pH 4.5.
 N. Fatin-Rouge, J.-C.G. Bünzli / Inorganica Chimica Acta 293 (1999) 53–60 57

dC13(ppm)= k× cos u× exp(−c ×r) (1)

Scheme 1. Top: numbering of carbon atoms in the a-CD glucopyra-
nose residue. Bottom: schematic representation of the host guest
position in the inclusion complex between a-CD and La3 + cation.
3+
in which k and c are positive constants. If La sits in
the vicinity of C5, the angle u is such that cos u is
negative, henceforth the shielding of C5. Chemically
speaking, this can be explained both with an internu-
clear repulsion between La3 + (or its hydration sphere)
and the H5 protons. The large steric polarization effect
on the C5 –H5 bond indicates that the angle (C5 –H5 –
La) is close to 180° and, on the other hand, the less
intense de-shielding of the H3 protons and a weak steric
polarization effect on the C3 –H3 bond are consistent
with a longer H3 –La distance and a C3 –H3 –La angle
close to 90°. To substantiate this interpretation we have
performed molecular mechanic calculations of the Y3 + /
a-CD interaction with the AM1 package [34]. They
show the cation positioned at the level of the C5 carbon
and of the anomeric oxygen atoms inside the cavity.
The reason for this positioning could be due to direct
(or to hydrogen bonded) interactions with the anomeric
oxygen atoms of the host. Analyzing the positions of
the C1 – 6 carbon atoms in the conically shaped a-CD we
get, as expected, a shielding for C5 and C6, and a
de-shielding for C2 and C3. The insertion of the Ln3 +
ions into the cavity induces some conformational
changes which are further reflected in variation of the
chemical shifts of C1 and C4, as reported for aromatic
host inclusion [32]. The lifetimes of the Eu(5D0) and
Tb(5D4) levels remain unchanged upon addition of one
equivalent CD to acidic solutions of the aqua ions
(0.1139 0.002 and 0.449 0.02 ms, respectively), which
means that the included cations are hydrated com-
pletely and that the Ln3 + –CD interaction is mainly an
outer-sphere process.

3.2. Association between tri6alent Tb and a-CD in

basic medium

Above pH 10, deprotonated secondary hydroxyl

Fig. 4. Top: Part of the 13C NMR spectra of a-CD in D2O/H2O
50/50 v/v at pH 4.5 in absence and in presence of La3 + ; R =[La3 + ]t /
[a-CD]t : 0 (a), 0.25 (b), 0.5 (c), 1 (d), 1.25 (e), 2 (f); [a-CD]tot =0.02
M; the chemical shifts are referenced with respect to external
methanol. Bottom: Variation of 13C chemical shifts with R.
groups of CDs were demonstrated to be able to bind
metal cations [35–38]. In our case, complexation of
terbium by partially deprotonated a-CD was detected
in a 0.002 M equimolar solution of the metal and the
host at pH\ 10.5. We have investigated the nature of
this interaction by spectrophotometry and NMR spec-
troscopy. A pH of 12.30–12.33 was chosen because it is
close to the average pKa of the host (12.33) and it

Table 3
Variation of the 1JCH coupling constants of a-CD upon La3+ addition (D2O/H2O 50/50 v/v, pH 4.5, 20°C)

Eq. of La3+ 1
JCH (Hz)

C1H1 C2H2 C3H3 C4H4 C5H5 C6H6

0 168.00 147.46 142.32 145.98 140.85 143.4

2 168.73 145.60 145.25 143.80 147.46 144.52
D(1JCH) (Hz) 0.73 −1.86 2.93 −2.18 6.61 1.1
58 N. Fatin-Rouge, J.-C.G. Bünzli / Inorganica Chimica Acta 293 (1999) 53–60

Fig. 5. Absorbance variation at 230 nm during the spectrophotomet-

ric titration of partially deprotonated a-CD with Tb3 + in D2O/H2O
50/50 v/v, pH 12.309 0.05, T= 25.090.1°C, l= 0.1 cm, [a-CD]0 =
9.2× 10 − 3 M.

allows us to use a simpler model for the interpretation

of the experimental data. The absorption spectra dis-
play an isosbestic point at 211 nm up to [Tb]tot/[a-
CD]tot =0.92. Beyond this ratio, the absorbance
increases linearly with the addition of the metal salt and
some turbidity appears for ratios R larger than 1. The
Fig. 6. 13C NMR titration curves for the addition of Tb3 + to
metal ion addition induces an absorption band at 230 partially de-protonated a-CD in D2O/H2O 50/50 v/v at pH 12.33 9
nm, corresponding to the 4f 8 “4f 75d transition of 0.03.
Tb3 + . Absorbance variations recorded at this wave-
length versus the number of metal equivalents clearly 13
C NMR titration of a-CD by Tb3 + at pH 12.33 in
points to a 1:1 stoichiometry of the complex (Fig. 5), in
D2O/H2O 50/50 v/v confirms the stoichiometry of the
agreement with the findings of Yashiro et al. for Pr3 +
complex (Fig. 6), but contrary to what was observed
[16]. Factor analysis of the spectrophotometric data
with transition metal ions, chemical shift variations
concluded to the presence of three main absorbing
point to a Tb3 + ion associated to the deprotonated
species, that we label Tb(aq), a-CD(aq) and [Tb(a-
secondary OH-3 hydroxyl function of the host
CD)](aq), since the exact composition and charges of
molecule: the C1 and C3 carbon atoms are de-shielded
these species cannot be determined. The following ap-
and their chemical shifts increase linearly up to R:1.
parent complexation constant (see Eq. (2)) was ob-
We interpret this as follows. At pH 13, the carbon
tained from the least-squares fit: log Kapp =4.24 90.06.
atoms of a-CD are de-shielded (0.42 ppm for C1), an
For each wavelength, the sum of residual absorbances
effect resulting from a conformational change [40].
was less than 0.025 and residues were dispersed ran-
Indeed, the first de-protonation occurs at the OH-2
domly. The fit yielded a molar absorbance coefficient
positions [41], so that the H–O(2)···H–O(3) hydrogen
o 230 nm = 430920 M − 1 cm − 1 typical of TbIII com-
bonds between adjacent glucosic units [42] are short-
plexes in water [39].
ened, resulting in a reduction of the larger ring section.
Therefore, a-CD is undergoing a conformational
Tb(aq)+ a-CD(aq) = [Tb(a-CD)]aq change, from its conical conformation in the fully pro-
tonated form to a cyclindrical conformation in the
[Tb(a-CD)] de-protonated form (Fig. 7). X-ray structures of metal
Kapp = (2) complexes with de-protonated a-CD evidence this con-
[Tb]·[a-CD]

Fig. 7. Schematic representation of the conformational changes occurring for a-CD upon de-protonation and subsequent complexation.
 N. Fatin-Rouge, J.-C.G. Bünzli / Inorganica Chimica Acta 293 (1999) 53–60
formation [36]. At the pH at which the Tb3 + titration
has been performed, all the OH-2 groups are de-proto-
nated so that the additional de-shielding of C1 (0.3
ppm) point to a further conformational change. Model
considerations show that an inverted cone structure in
which the OH-3 groups are orientated conveniently to
bind Tb3 + is the most probable. Lifetime measure-
ments of the Eu(5D0) and Tb(5D4) excited levels upon
addition of one equivalent CD (tEu =0.230 ms and
tTb =1.08 ms, as compared to 0.113 and 0.442 ms,
respectively, for the aqua ions [43]) reflect the loss of
3 – 4 inner-sphere water molecules upon complexation.
This result is consistent with the 13C NMR data and
model considerations which suggest that several coordi-
nating groups located at the O-3 position of the par-
tially deprotonated CD enter the first coordination
sphere of the cation.
4. Conclusion
Several factors are invoked usually to account for the
association of CDs with various molecules [44]. In this
work, we have demonstrated that at acidic pH, an
entropically driven inclusion of trivalent Ln cations
occurs with the three native a-, b-, and g-CDs, leading
to 1:1 complexes with log K in the range 2 – 4. NMR
analysis shows the metal ion coordinated to anomeric
O-atoms of a-CD in the vicinity of the C5 carbon atom.
On the other hand, in basic medium, partially deproto-
nated a-CD molecules seem to act as first sphere coor-
dination ligand and the formation of a 1:1 complex
with trivalent terbium is accompanied by a large reor-
ganization of the host molecule, so that the bonding
can be considered as being on the outside of the
cyclodextrin. In both kinds of complexes hydrogen
bonds probably play a major role in stabilizing the
supramolecular structures. This opens interesting per-
spectives for the protection of Ln containing species
against solvent interaction by native or derivatized
CDs.
Acknowledgements
This work is supported by grants from the Swiss
National Science Foundation. We thank the Fondation
Herbette (Lausanne) for the gift of spectroscopic equip-
ment and V. Foiret for measuring the luminescence
lifetimes.
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