856 Macromolecules 2004, 37, 856-862 Lanthanide Ion Interaction with a Crown Ether Methacrylic Polymer, Poly(1,4,7,10-tetraoxacyclododecan-2-ylmethyl methacrylate), as Seen by Spectroscopic, Calorimetric, and Theoretical Studies M. J. Tapia,*,† H. D. Burrows,‡ J. M. Garcı´a,† F. Garcı´a,† and A. A. C. C. Pais Departamento de Quı´mica, Universidad de Burgos, Plaza Misael Ban˜ uelos s/n, Burgos 09001, Spain, and Departamento de Quı´mica, Universidade de Coimbra, 3004-535 Coimbra, Portugal Received September 17, 2003; Revised Manuscript Received November 17, 2003 ABSTRACT: The interaction between trivalent lanthanide ions and the polymer poly(1,4,7,10-tetraoxa- cyclododecan-2-ylmethyl methacrylate) (PCR4) containing pendant 1,4,7,10-tetraoxacyclododecane (12- crown-4) groups has been studied by various spectroscopic techniques, calorimetry and theoretical calculations. Evidence for the binding of Eu(III), Tb(III), and Ce(III) ions and PCR4 in solution was obtained by the lanthanide-induced 1H and 13C NMR shifts and the decay of Tb(III) luminescence. From the isotope effect observed on the decay of luminescence of Tb(III) bound to PCR4 in H2O and D2O solutions, it is suggested that complexation leads to a decrease in the number of water molecules from 8 or 9 to 7. In the solid state, studies by differential scanning calorimetry (DSC) show that the interaction between Ce(III), Tb(III), and Li(I) ions and PCR4 leads to an increase in the glass transition temperature (Tg)of the polymer. Electron paramagnetic resonance (EPR) spectra of Gd(III) in the presence of the polymer are quite similar to those in aqueous solution, while Tb(III) emission is quenched by Ce(III) with nearly the same rate constants in water and aqueous PCR4 solutions, and the Ce(III) emission maxima are only very slightly shifted in the presence of the polymer, all suggesting relatively weak dynamic interaction between the cations and the crown ether. However, isotope effects on the Tb(III) luminescence lifetime confirm complexation. From the lanthanide-induced 1H and 13C NMR shifts the stability constants of the 1:1 complexes formed have been calculated for both Tb(III) and Eu(III), yielding values 22.5 and 1.9, respectively. The agreement between the constants calculated from 1H and 13C NMR shifts are very good and the low values of the calculated stability constants confirm the weak binding of the lanthanide ions by the crown ether. Results of ab initio calculations are also reported, where the interactions are modeled for 12-crown-4/La(III) complex and bond energies determined. Introduction lysts,6 and so on, related to the fact that crown ether In 1967 Charles J. Pedersen published two papers can selectively recognize alkali, alkaline earth metal describing the binding of alkali metal ions (lithium, ions, and other cations, including lanthanides, actinides, sodium, potassium, rubidium, and cesium) to com- and transition metals. Considering the dependence that pounds he called crown ethers.1,2 These compounds are many of these potential technological applications of the cyclic polyethers made up of ethylene glycol units, polymer-bound crown ethers have on their interaction with metal ions, it is of great interest to study the (OCH2CH2)n, while the name crown derives from the appearance of space filling models of the compound and interaction between metal ions and crown ether poly- the ability of these compounds to “crown” cations. These mers directly. However, the problem at the molecular compounds have attracted the attention of chemists over level with alkali and alkaline earth ions is the limited the last 30 years, and the importance of crown ethers number of spectroscopic properties available to study and related compounds has been recognized with the polymer-metal interaction. In this respect, trivalent award of the 1987 Nobel Prize to Professors Pedersen, lanthanides are very useful tools because, on one hand, Cram, and Lehn for their pioneering work in this area. they can replace metal ions such as Ca(II), Zn(II), The ability of organic molecules to bind metal ions is Mg(II), Mn(II), Fe(II), and Fe(III) in many systems, not limited to the free crown ethers, such as 1,4,7,10- including biological ones, where they have been shown tetraoxacyclododecane (12-crown-4). Polymers with pen- to provide information about the biochemical processes,7 dant crown ethers are of considerable interest and and at the same time they are observable by a variety importance and are expected to show different selectiv- of spectroscopic techniques.8 In nuclear magnetic reso- ity from their monomers in complex formation with nance spectroscopy (NMR), lanthanides are used as shift metal cations. Much of the main focus of crown ether reagents.9,10 In addition, Gd(III) can act as an electron structures is now directed toward the inclusion of these paramagnetic resonance (EPR) probe.11 Further, they supramolecules in a polymer matrix or in a polymer exhibit excellent electronic properties which makes structure due to the enormous possibilities these sys- them valuable as luminescent probes.8,12,13 Several tems present in high technology applications, such as, studies have already been presented using lanthanides sensors,3 actuators,4 permselective membranes,5 cata- as probes in crown ether polymers.14,15 Recently, we have reported detailed studies of the † Universidad de Burgos. interaction of lanthanides with different surfactant and ‡ Universidade de Coimbra. polymeric systems, using mainly luminescence and EPR * To whom correspondence should be addressed. Facultad de Ciencias. Telephone: 0034 947 258061. Fax:0034 947 258831. techniques. In particular, we have studied interaction E-mail: [email protected]. of these cations with sodium dodecyl sulfate (SDS) 10.1021/ma0353888 CCC: $27.50 © 2004 American Chemical Society Published on Web 01/06/2004 Macromolecules, Vol. 37, No. 3, 2004 Lanthanide Ion Interaction with PCR4 857 and luminescence spectroscopic techniques have been used. The chemical shift increments in the 1H and 13C NMR spectra permit calculation of the stability con- stants of the complexes formed. In addition, cation- polymer interaction in the solid state has been evaluated using DSC measurements. Finally, some ab initio calculations have been per- formed to allow a qualitative evaluation of the energetic stabilization induced by the metal-ion interaction. Materials and Methods Reagents. Cerium(III), terbium(III), europium(III), and gadolinium(III) perchlorates (40% water solution) and deu- terium oxide (99.9%) were purchased from Aldrich and used without further treatment. Millipore-Q water was used to prepare all solutions. Apparatus and Methods. For steady-state luminescence spectral measurements, a Shimadzu RF-5301 PC instrument was used in right-angle configuration. Tb(III) luminescence lifetimes were measured using the Spex 1934D phosphorim- eter accessory with a Jobin-Yvon-Spex Fluorolog 3-22 in- strument, and decays were analyzed using Origin 5.0 soft- ware. Electron paramagnetic resonance measurements were carried out in aqueous solutions with samples in the sealed capillary part of Pasteur pipets; all spectra have been corrected for the background signal of the glass. Spectra were recorded on a Bruker EMX10/12 spectrometer, equipped with Bruker 13 1 N2 temperature controller device BVT3000, operating at X Figure 1. Structure of PCR4, together with and C and H band and calibrated with DPPH (R,R′-dipheyl-â-picrylhydra- NMR spectra (upper and lower spectra, respectively) and zyl). The NMR spectra of polymers were recorded on a Varian signal assignments. INOVA 400 spectrometer operating at 399.92 MHz (1H) and 13 100.57 MHz ( C), using D2O or CDCl3 as solvent. All lumi- micelles,16 bis(2-ethylhexyl) sulfosuccinate (AOT)/water/ nescence, NMR and EPR spectra have been registered at 20 isooctane microemulsions,17 and the polyelectrolyte °C. The thermal properties of the polymer and lanthanide- sodium poly(vinyl sulfonate) (PVS).18 The systems stud- polymer complex were determined calorimetrically with a ied so far have all been anionic. We extend these studies Perkin-Elmer Pyris I calorimeter at a heating rate of 10 °C - to consideration of the interactions of lanthanide cations min 1. with an uncharged water-soluble polymethacrylate Synthesis of Monomer and Polymers. 1,4,7,10-Tetraoxa- containing a pendant 12-crown-4 ether structure. We cyclododecan-2-ylmethanol and 1,4,7,10-tetraoxacyclododecan- 2-ylmethyl methacrylate (CR4MA) were prepared according have chosen the poly(1,4,7,10-tetraoxacyclododecan-2- 20 ylmethyl methacrylate), because the discrete 12-crown-4 to the synthetic procedures described by Tiemblo et al. and Garcı´a et al.21 The radical polymerization of CR4MA to form molecule is one of the best and most widely studied PCR4 and the subsequent purification were accomplished crown ethers in metal extraction and both the polymer following the procedure described by Garcı´a et al.22 - and the polymer metal complexes are water soluble Polymer Characterization. The structure of the polymer 19 which facilitates the extractability. This makes the PCR4 (Figure 1) was confirmed by 1H and 13C NMR spectros- study of crown ether-metal interaction particularly copy. The tacticity of the polymer was determined by 13C NMR interesting. Although, this is not the optimum size spectroscopy: an average molar fraction of syndiotactic diads (crown-4 cavity size radii, 60-75 pm)19 for incorporating of 0.83 ( 0.05 was obtained. Comparison of this with the values lanthanide ions (ionic radii, around 95 pm), it provides of the triad and pentad units indicates Bernoullian stereo- a good starting point for a systematic study on the chemical control.23 The predominance of syndiotactic over isotactic sequences is similar to that found for other meth- interaction between these cations and polymer based 24 crown ethers. Similar compounds but with larger crown acrylic polymers.