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nl/locate/ica 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. Bunzli * ¨
Uni6ersite de Lausanne, Institut de Chimie Minerale et Analytique, Unite de Recherche sur les Elements 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 (v= 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 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  and the second provide speciﬁc and protective micro-environments for small molecules included in their cavity [4,5]. Lanthanide-centered luminescence is easy to sensitize by the antenna effect , but avoiding de-activation through high energy vibrations of bound ligands or of solvent molecules is more difﬁcult . Indeed, small water molecules interact strongly with Ln3 + ions and the design of a coordination environment bearing chromophores suitable for an efﬁcient antenna effect and protecting the LnIII ions from water
* Corresponding author. Tel.: + 41-21-692 3821/3850; fax: +4121-692 3825. E-mail address: email@example.com (J.-C.G. Bunzli) ¨
complexation remains a challenge for synthetic 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  led to the design of efﬁcient supramolecular devices and architectures [5,10,11]. CDs can also include coordination complexes  with sizable binding constants as large as 2000 M − 1 . They are expected to reduce deactivation 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 . For these reasons, we have launched a research program aiming at investigating second sphere Ln3 + complexation 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
accuracy 0. results . was used along with a Metrohm 6.1 M) than the solutions to study in order to minimize junction potentials.0090. Fatin-Rouge. Rhone Poulenc).5°. 100 nm min − 1 scan-speed) using 0. Titration of a 0.and g-CDs in basic medium . Stock solutions of CDs ( 8 mmol l − 1) were prepared from freshly boiled doubly distilled water saturated with N2. NMR measurements 1 H and 13C spectra were collected on DPX-400 or AM-360 Bruker spectrometers.02 (HCl) at least 30 min before titration. of CD . band g-CDs. we report thermodynamic and structural data on the insertion of La3 + (aq) in a-. The data (60 points per curve. accuracy 0. Under these conditions. The following values of the ionic product of water were taken into account (v= 0.0°C (205–500 nm.0 9 0. 2.-C.1 ml) program and linked to an IBM PS/2 computer.3 ml of solution was transferred into a quartz cell with a Teﬂon® syringe. The following Metrohm buffer solutions were used to calibrate the electrode: 62305. pH 4) was performed at pH 12.72 (NaCl ) and pKw =13.3013. b-. as well as of the association of Tb3 + (aq) with a-CD at basic pHs. Care was exercised to analyze the pH domain in which CDs are non deprotonated. the electrode was used 48 h after conditioning. Na2CO3.1°C) glass jacketed vessel and under Ar atmosphere. Reactants were mixed in the thermostated vessel and acidiﬁed to pH 4. Experimental 2. NaHCO3 (Merck). The a-CD titration with La3 + (aq) in acidic solution was monitored by 13C NMR as follows: ﬁve samples of a-CD 0. b-CD =162.00). pH Potentiometry The hydrolysis constants of Ln3 + and the association constants with non deprotonated CDs were determined by pH potentiometric titrations of 0. Bunzli / Inorganica Chimica Acta 293 (1999) 53–60 ¨ mental data on Ln3 + – CDs interaction. standardized Na2H2EDTA solution in urotropine buffered medium was used along with xylene orange as indicator. Titrations were carried out with an automatic Metrohm Titrino 736 GP potentiometer (resolution 0. The ionic strength of the solutions was held constant (v =0. tetramethylammonium hydroxide (TMAOH) (Fluka).0 ml addition. pH 10.107 g. 1H NMR spectrum of a-CD was assigned following Woods et al.000 glass electrode. In this paper.1. to avoid hydroxide precipitation. Chemical shifts of a-CDs H2-6 protons were obtained using selective irradiation. Spectrophotometric titrations Electronic spectra were recorded with a Perkin– Elmer l-900 spectrophotometer at 25.5 9 0. Na2B4O7. An automatic burette (Metrohm 2. The latter was prepared with the same electrolyte and at the same ionic strength (0.93 (TMACl). NaCl or TMACl.1°C) glass-jacketed vessel under Ar atmosphere. The Ln3 + solution was added with fast mixing to avoid local excess and precipitation. Both the LaIII .99%. tetramethylammonium chloride (TMACl).3090.00).5° and g-CD = 177. They were acidiﬁed systematically with HCl to pH 4 before complexometric titration. 10 ml. but for one partial study on the dissolution of praseodymium hydroxide by a.05 in a thermostated (25. 1H NMR spectra were recorded in D2O and 13C spectra were recorded in H2O/D2O 50/50 v/v using methanol as external reference.025 M Na2CO3-NaHCO3 (v=0. Assignment of the 13C spectra was done using 1H decoupling.009 M a-CD solution (20 ml) by Tb(ClO4)3·nH2O (0.010 (pH 4. ˆ Ln3 + solutions were prepared just before use from freshly boiled doubly distilled water saturated with N2.5). Stock solutions of Ln(ClO4)3 ( 8 mmol l − 1) were prepared from lanthanides oxides (99.1 M) by adding an aliquot of NaCl or TMACl. 62305.5° ).0238. J.1 cm quartz cells.5 M.1 M. before 0.00).05 M (0.0°C (a-CD =150.210.3.G. drift 1 mV mn) were treated mathematically by the program SUPERQUAD  using a Marquardt algorithm. Substances used for 1H NMR were dried under vacuum after dissolution in D2O.467 M. we have started our study by looking at inclusion complexes of Ln3 + aqua-ions with native CDs. as determined from HCl–TMAOH titration.4. The [Tb3 + ]/[a-CD] ratio ranged from 0 to 1. traces of silver nitrate were added and after measurement the electrode was left in an acidic solution (HCl. and 0. equilibrium was attained within 10 min. NaCl.03 ml).09 0.54 N. 2. and g-CD and of Ln3 + (aq) in a-CD in acidic solutions. 2 ml) were prepared and La(ClO4)3·nH2O was added to yield [La3 + ]t / [a-CD]t ratios ranging between 0 and 2.1 mV. A 15 min time delay was imposed after each 20. Sol6ents and stating materials All the chemicals used in this study were of analytical grade and were used without further puriﬁcation: a-.1 M): pKw = 13. The apparent complexation constant was determined using the SPECFIT program .01 ).3.2 mV) using a constant volume addition (0. The pH was maintained constant during the titration by addition of KOH 0. The concentrations of CDs were calculated from the optical rotation of sodium light at 25. 62305.2.5 9 0. 6. 2. The titrations were carried out using 20 ml sample solutions in a thermostated (25.590.020 (pH 7. pH 2. DEPT (distortionless enhancement by polarization transfer) 135  and previously published results .020 (pH 9.002 M metal solutions in absence and in presence of 1 equiv.
a special model was adopted for La3 + .and g-CDs on the other hand. Examination of Fig. 1.8 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 − 1.5 ml were syringed from the titration vessel for analysis.2 ml.e. pH 12.034 M. respectively.0 90. 0.8–4 (Table 1) and appear to be almost independent of the nature of the receptor despite variations in diameter  and polarity  of the cavity.15 M in H2O/D2O 50/50 v/v. Potentiometric titration curves of La3 + (top) and Lu3 + (bottom) ions in absence (1) and in presence of a-CD (2). The pH-potentiometric titration of Ln3 + ions alone gave accurate values of the acidic hydrolysis constants. . DH =28. The pH was adjusted to 4. Analysis of the pH titration curves obtained in presence of one equivalent of CD was made introducing an association constant  between the Ln3 + cation and CDs: K = [Ln3 + ·CD]/[Ln3 + ]·[CD].N. pH values were measured using a calibrated glass electrode in H2O/D2O 50/50 v/v with KOH solution. taking into account partially deprotonated a-CDs. 2. for both b. means that CDs do not exchange protons in the pH range analyzed. The association constants with the three CDs are in the range log K=3. which increased with further metal addition and these were ﬁltered before analysis. b-CD (3). Lifetime determination Eu(5D0) and Tb(5D4) lifetimes were measured on solutions 0. Bunzli / Inorganica Chimica Acta 293 (1999) 53–60 ¨ 55 salt and the a-CD were titrated just before measurement to determine their exact hydration number. the pKa value of which is especially large. [TMAOH]tit = 0. g-CD (4). Data are averages of 3 – 5 determinations.09. Below pH 10. Decay curves were treated mathematically on an IBM PS/2-80 computer using a home made algorithm. 1.5 K).090. Enthalpy (DH) and entropy (DS) changes were estimated from the temperature dependence of K in a limited temperature range (298.025–0. [Ln3 + ]0 =[CD]0 =0. 1 shows that titration curves for La3 + display some difference between a-CD on one hand and b. which Fig. The pH and the solvent composition were adjusted and 0.1°C (the starting pH value was reached by adding acid before titration).G.1.33 90.1 M in both bidistilled and degassed water and deuterated water. Results and discussion 3.5 M − 1 versus 30 – 50 M − 1 for ClO4 ). For a-CD. A chloride salt was chosen as electrolyte because this anion has the smallest association constant with CDs − (for a-CD.002 M.591. These 3. addition of CD to the solutions did not inﬂuence the number of base equivalents needed to titrate the Ln3 + ions.5. Fatin-Rouge.1°C in a glass jacketed vessel under Ar atmosphere.and g-CDs.5 nm) or 5D0 7F1 transition (588 nm) while coumarine 102 was used to excite Tb through its 5D4 7F6 transition at 488 nm. V0 =20 ml. g-CD) monodeprotonated CD accounts for less than 5% and no complex between this species and La3 + ions was detected. v= 0. 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. This model ﬁtted conveniently the titration curves and except for La3 + (aq). very close to the literature values . speciation diagrams show that in the worst case (i.03) thermostated at 25. A slight turbidity appeared for [Tb3 + ]t /[a-CD]t \ 1. Tb(ClO4)3·nH2O 0.467 M in H2O was added to a solution of a-CD (7.2–310. 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. T=25. Therefore.1 M (TMACl). Rhodamine 6G was used for Eu which was excited though the 5D0 7F0 (578.-C. For titration in basic medium.5 using 1 to 7 ml of H2SO4(aq) and a glass electrode. J. The signal was averaged with a SR-430 multichannel scaler coupled to a SR-400 gated photon counter from Stanford Research Systems. pulse width: 18 ns).
which reﬂects some competition between Ln3 + and Na + .1 M TMACl) T (K) 298.23 (9) 3. + 0.45 −21. and + 0.28 −23. we have recorded 1H and 13C NMR spectra at pH 4.7 (1) 2.21 −22. of La3 + (b) at pH 4. H3.86 −20.68 −20. Association constants of Ln3 + cations with a-CD as determined by competitive potentiometric titrations at 25. + 0.85 (6) 3.61 −21. leading to identical values of log K.18 (7) 2.0 (1) 3. To determine whether the Ln3 + – CD association occurs on the outside or inside the host cavity. H4.5 91.91 9 0.12 3.78 −22.97 90.77 9 0.74 −22. titration curves with the three CDs are superimposable. the reciprocal of the ionic radii for a coordination number of 9 . b-. the H5 and C5 chemical shifts varying in opposite direction upon metal addition.79 (9) 2.12 3.65 (9) 2. T= 25. for which K is the largest.1 M (NaCl).98 (4) 2. H6a and H6b. J.0 (1) 3. In view of the low dependence of K(Ln3 + ) upon the host. A plot of these constants versus the inverse ionic radii for coordination number 9 (Fig.6 (1) 2.859 0.059 0.105.8 1699 6 b-CD 3.97 9 0.08 −22. 2) displays variations along the lanthanide series which are reminiscent of a tetrade effect  and which point to the inﬂuence of solvation and coordination number change on the association process. Bunzli / 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-.0 302.09 0. they show that carbon atoms C5 have the largest chemical shift variation and become shielded (Fig. and g-CDs (H2O.10 28. we have examined the 13 C NMR spectra and indeed.5 DH (kJ mol−1) DS (J K−1 mol−1) a-CD 3.71 b* =[Ln(OH)3]·[H3O+]3/[Ln3+].10 4.32 −22.1 M (TMACl) log b* 1–3 −26. − 0.5 (1) 2. respectively (see Scheme 1). Fatin-Rouge.54 −22.88 −22. + 0. which are localized in the narrow part of the conically shaped CD. The largest variations occur for the internal protons H3 and H5 and similarly to what was observed for aromatic guest inclusion . 2.0 310.1°C.12 3. .78 (9) 3. vs.40 (7) 3. 3.46 (9) 2.14 3.14 3. thermodynamic parameters are indicative of an entropically driven association. − 0.3 (1) −26.0 90.-C.12 29 9 4 169 9 16 Fig. These data are consistent with steric polarization . Large and positive values for DH point to a weak metal – ligand interaction energy as expected for complexation by neutral donor atoms.020.8 (1) 2. Moreover.6 (1) 3.016. we apply the theory of steric polarization of C–H bonds by a proton H% to the system C5 –H5 –La3 + (Scheme 1). To conﬁrm this assignment.1 M (NaCl) log b* 1–3 La Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu a v =0.56 N.41 −24. 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).0 (2) 5.779 0.91 (8) 2.77 (8) 3.12 2994 1699 16 g-CD 3. 1–3 Fig. association constants for the entire Ln3 + series were determined with a-CD only (Table 2).78 (9) 3.34 −22.76 −22. H2.11 −21. For Lu3 + .44 (9) 2. these protons are de-shielded upon addition of La3 + (aq).25 (8) 3. 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.66 (8) 3.82 9 0.5.04 (5) (4) (5) (5) (5) (5) (5) (5) (4) (5) (6) (7) (8) log K 3.46 −21. the association constants are slightly larger when TMACl is used as inert electrolyte instead of NaCl. For R = Table 2 Hydrolysis constants (log b* ) a of Ln3+ ions and association con1–3 stants (log Kass) with a-CD (H2O.1°C). H5.12 −24.72 −21.G.16 −21.011. 92s indicated within parentheses Ln v= 0. 4).00 −23.040. Part of 1H NMR spectra of a-CD alone in D2O (a) and in presence of 5 equiv.97 −21. To explain these data more quantitatively. 3).5 in D2O as a function of R =[La3 + ]tot/[a-CD]tot (Fig.009 for H1. The 13C chemical shift (lC13) is a function of the angle C–H–La (q) and of the H–La distance (r) : log K (5) (4) (4) (4) (5) (5) (4) (4) (6) (5) (8) (6) (6) 3. Except for La3 + .20 (9) 3. v= 0. the following chemical shift differences were observed: − 0.014.82 90. v = 0.14 −22.33 −20.74 (9) 3.
00 168. They show the cation positioned at the level of the C5 carbon and of the anomeric oxygen atoms inside the cavity.93 C4H4 145.46 6. pH 4. which means that the included cations are hydrated completely and that the Ln3 + –CD interaction is mainly an outer-sphere process.46 145.5 in absence and in presence of La3 + . 3. 1 (d). this can be explained both with an internuclear repulsion between La3 + (or its hydration sphere) and the H5 protons.52 1.5. 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°. Bottom: schematic representation of the host guest position in the inclusion complex between a-CD and La3 + cation. Chemically speaking.25 (b).73 . We have investigated the nature of this interaction by spectrophotometry and NMR spectroscopy. 2 (f).86 C3H3 142.32 145.02 ms.-C.449 0. the chemical shifts are referenced with respect to external methanol. as reported for aromatic host inclusion . Top: numbering of carbon atoms in the a-CD glucopyranose residue.002 M equimolar solution of the metal and the host at pH\ 10. In our case. R =[La3 + ]t / [a-CD]t : 0 (a). Fatin-Rouge. deprotonated secondary hydroxyl groups of CDs were demonstrated to be able to bind metal cations [35–38]. henceforth the shielding of C5.60 −1. complexation of terbium by partially deprotonated a-CD was detected in a 0.4 144.80 −2.25 (e).5 (c).30–12. The reason for this positioning could be due to direct (or to hydrogen bonded) interactions with the anomeric oxygen atoms of the host. of La3+ 1 JCH (Hz) C2H2 147. the angle q is such that cos q is negative. The large steric polarization effect on the C5 –H5 bond indicates that the angle (C5 –H5 – La) is close to 180° and. 20°C) Eq. 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 C4.61 C 6H 6 143.1139 0.N.G. [a-CD]tot =0. a shielding for C5 and C6. 4. as expected.2. 0. in which k and c are positive constants. respectively). 1.5.18 C5H5 140.33) and it Fig.73 0. If La3 + sits in the vicinity of C5. Bottom: Variation of 13C chemical shifts with R. A pH of 12.33 was chosen because it is close to the average pKa of the host (12. and a de-shielding for C2 and C3.25 2. Table 3 Variation of the 1JCH coupling constants of a-CD upon La3+ addition (D2O/H2O 50/50 v/v. Top: Part of the 13C NMR spectra of a-CD in D2O/H2O 50/50 v/v at pH 4.02 M. Association between tri6alent Tb and h-CD in basic medium Above pH 10. Analyzing the positions of the C1 – 6 carbon atoms in the conically shaped a-CD we get.1 C1H1 0 2 D(1JCH) (Hz) 168. 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 (0.002 and 0. Bunzli / Inorganica Chimica Acta 293 (1999) 53–60 ¨ 57 lC13(ppm)= k× cos q× exp(−c ×r) (1) Scheme 1. on the other hand.85 147.98 143. 0. J. To substantiate this interpretation we have performed molecular mechanic calculations of the Y3 + / a-CD interaction with the AM1 package .
Indeed. the carbon atoms of a-CD are de-shielded (0.-C. so that the H–O(2)···H–O(3) hydrogen bonds between adjacent glucosic units  are shortened.G. The absorption spectra display an isosbestic point at 211 nm up to [Tb]tot/[aCD]tot = 0.2× 10 − 3 M. a-CD is undergoing a conformational change. 7. that we label Tb(aq). Schematic representation of the conformational changes occurring for a-CD upon de-protonation and subsequent complexation. Bunzli / Inorganica Chimica Acta 293 (1999) 53–60 ¨ Fig. [a-CD]0 = 9. Fatin-Rouge. Tb(aq) + a-CD(aq) = [Tb(a-CD)]aq Kapp = [Tb(a-CD)] [Tb]·[a-CD] (2) Fig. .1°C.309 0.24 90. resulting in a reduction of the larger ring section.03. allows us to use a simpler model for the interpretation of the experimental data. 7).1 cm. The following apparent complexation constant (see Eq. 6). At pH 13. The metal ion addition induces an absorption band at 230 nm. Beyond this ratio. since the exact composition and charges of these species cannot be determined. an effect resulting from a conformational change . X-ray structures of metal complexes with de-protonated a-CD evidence this con13 Fig. u= 0. chemical shift variations point to a Tb3 + ion associated to the deprotonated secondary OH-3 hydroxyl function of the host molecule: the C1 and C3 carbon atoms are de-shielded and their chemical shifts increase linearly up to R:1. 13C NMR titration curves for the addition of Tb3 + to partially de-protonated a-CD in D2O/H2O 50/50 v/v at pH 12.33 9 0. We interpret this as follows. Factor analysis of the spectrophotometric data concluded to the presence of three main absorbing species. in agreement with the ﬁndings of Yashiro et al. the sum of residual absorbances was less than 0.33 in D2O/H2O 50/50 v/v conﬁrms the stoichiometry of the complex (Fig.025 and residues were dispersed randomly. but contrary to what was observed with transition metal ions. 6. The ﬁt yielded a molar absorbance coefﬁcient m 230 nm = 430920 M − 1 cm − 1 typical of TbIII complexes in water .090. Therefore.58 N. For each wavelength. J. for Pr3 + . Absorbance variations recorded at this wavelength versus the number of metal equivalents clearly points to a 1:1 stoichiometry of the complex (Fig. 5. Absorbance variation at 230 nm during the spectrophotometric titration of partially deprotonated a-CD with Tb3 + in D2O/H2O 50/50 v/v. 5). the absorbance increases linearly with the addition of the metal salt and some turbidity appears for ratios R larger than 1. C NMR titration of a-CD by Tb3 + at pH 12.92. T= 25.05.42 ppm for C1).06. pH 12. the ﬁrst de-protonation occurs at the OH-2 positions . from its conical conformation in the fully protonated form to a cyclindrical conformation in the de-protonated form (Fig. (2)) was obtained from the least-squares ﬁt: log Kapp =4. corresponding to the 4f 8 4f 75d transition of Tb3 + . a-CD(aq) and [Tb(aCD)](aq).
G. Khan. Inorg. as compared to 0. Popov. Model considerations show that an inverted cone structure in which the OH-3 groups are orientated conveniently to bind Tb3 + is the most probable. G. 96 (1974) 8081. 89 (1967) 5315. Yamamura. A. Rev. M.D. French. K.113 and 0. K. Chem. J. 106 (1997) 197.J.  J.E. Sabbatini. 123 (1993) 201. Vernon Cheney. 98 (1998) 1743. 39 (1998) 3481. Shiozuka. Rice. 33. Rudzinski. M. Modern NMR Techniques and Their Applications in Chemistry. Chem. 92 (1992) 1457. Sillen. Saenger. D’souza. Hruska. Inclus. J. Votgle.R.M.R. F. Foiret for measuring the luminescence lifetimes. Smith. E. Oxford.L. Amsterdam. Pazur. p. b-. Dalton Trans. Oxford. S.C. Gampp.A. 1998. Chem.230 ms and ~Tb =1.3 ppm) point to a further conformational change.08 ms. Rev.W. for the aqua ions ) reﬂect the loss of 3 – 4 inner-sphere water molecules upon complexation.  S. L. D. Zoebisch. Choppin. J.K. Atwood.N.H. Chim. T. Chem. Komiyama.G. Bunzli / Inorganica Chimica Acta 293 (1999) 53–60 ¨ 59 formation .E.  J. Recl. J. Engebreton. Choppin (Eds. A.S. J. vol.  L Szente. 5. Soc. Tabushi.  G.  P.P. Guardigli. 42 (1988) 1315.H. Lehn (Eds. D. Soc.M.  C. Connors. Inoue. Chem. Atwood. Soc. J. J.Z. Chem. Handbook on the Physics and Chemistry of Rare Earth.. Trav. Hallenga.G. (1985) 1195. Belg. 170 (1998) 31. vol. Immel. 5th ed. Lipkowitz. Gschneidner Jr. Chem. Lanthanide Probes in Life. Rev. S.D. Fatin-Rouge. Stoddart. G. A. Acknowledgements This work is supported by grants from the Swiss National Science Foundation. Majdan.  F. vol. M. Soc. Corridini. Lehn (Eds. de Silva. Takarada.  Y.-C.  M. Licchelli. Skoog. A. Dewar. 205. E. J. J.V. Chim. so that the bonding can be considered as being on the outside of the cyclodextrin. Maeder. respectively.T. N. D’souza.  K.A. Mac Nicol. Meyer. This result is consistent with the 13C NMR data and model considerations which suggest that several coordinating groups located at the O-3 position of the partially deprotonated CD enter the ﬁrst coordination sphere of the cation. B. Gans.P. Bergonzi.M. J. Chem. W. We thank the Fondation Herbette (Lausanne) for the gift of spectroscopic equipment and V. Acree. Yashiro. Coord.  D. Marchelli.  Y. Humbert. Matsui. W. K.  V. Part A.E. 27 (1993) 59. J. Soc. 25 (1996) 3. 37 (1998) 317. Am. Pays-Bas 107 (1988) 515. Spectrosc. E. pp. Street. Wang.  R. Sartor. 98 (1998) 1977. Nieman.A.M. At the pH at which the Tb3 + titration has been performed.P. Holler. Fabrizzi. Chem. Am.  A. Panagia. Elsevier Science. Lichtenthaler. V. Phenom. . Mac Nicol..J. L. Chem. I.J. J. Tetrahedron Lett. Hatmann. (Eds. W. Pergamon. 391. 274. in: E. Bull.M.J. Recogn. 617. partially deprotonated a-CD molecules seem to act as ﬁrst sphere coordination ligand and the formation of a 1:1 complex with trivalent terbium is accompanied by a large reorganization of the host molecule.J. 21. Zuberbuhler. 97 (1997) 1515. Phenom. J. On the other hand.E. Kang. In this work. Stewart.E. D. Soc.D. D.M. Dossena. Coord.). 99 (1977) 7100. Soc. Woods.  F. Am. Harcourt Brace College Publishers. Li.  L. J. Shimizu. W. This opens interesting perspectives for the protection of Ln containing species against solvent interaction by native or derivatized CDs.  H. Philadelphia. 1989. Vacca.  A. Chem. H. Monat.  D. T.B. ¨ Chemical and Earth Sciences.. 3.442 ms. Rep. Mangano. A. A. Elsevier Science.).  Y. Marcel Dekker.  P. D. Chem. Conclusion Several factors are invoked usually to account for the association of CDs with various molecules . Comprehensive Supramolecular Chem¨ istry. C. 1982. T. Soc. Hartmann. leading to 1:1 complexes with log K in the range 2 – 4. 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