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Inorganic Chemistry Communications xxx (2012) xxxxxx

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Inorganic Chemistry Communications


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Synthesis, crystal structures and competitive binding property of a family of functionalized calix[4]arene ionophores
Vallu Ramakrishna, Subrata Patra, E. Suresh, Anjani K. Bhatt, Pragnya A. Bhatt, Amjad Hussain, Parimal Paul
Analytical Science Division, Central Salt and Marine Chemicals Research Institute (constituents of CSIR, New Delhi), G. B. Marg, Bhavnagar 364002, India

a r t i c l e

i n f o

a b s t r a c t
A family of calix-crown hybrid molecules incorporating crown-4, crown-5 and crown-6 moieties as ionophore has been synthesized to evaluate their competitive complexing and extracting ability towards different alkali and alkaline earth metal ions. Selectivity of these ionophores towards Li+, Na+, K+, Ca2+, Mg2+ and Sr2+ has been evaluated with aqueous solution containing equimolar mixture of these ions. The concentration of metal ion in the extract (organic phase) has been estimated by ion chromatographic assay. Two of the ionophores show strong complexation with Na+ and K+, whereas the third ionophore exhibits no complexation with any metal ions used in this study. Association constants (Ka) for the binding of Na+ and K+ with two of these ionophores have been determined spectrophotometrically. Molecular structures of the Na+ and K+ complexes of these ionophores have been established by single crystal X-ray study. 1H NMR study of the ionophores and their complexes has also been carried out to investigate conformational behavior of the ionophores and their metal complexes in solution. Results have been discussed in light of various factors contribute to determine ionselectivity. 2012 Elsevier B.V. All rights reserved.

Article history: Received 5 January 2012 Accepted 15 May 2012 Available online xxxx Keywords: Calixarenes Ion-selectivity Crystal structure Binding constant Two-phase extraction

Calixarenes, which are macrocyclic oligomers made up of phenol units linked by methylene bridge, are receiving increasing attention because of their ability to bind variety of ions [17]. In the calixarene family, calix[4]arenes are most popular because of their rigid structures, which make them ideal candidates for the complexation with metal ions [116]. This chemistry has become even more versatile because of the ease with which calix[4]arene can be modied depending on the requirement. These modied calixarenes provide a highly preorganized architecture for the assembling of converging binding sites [1722]. Among these calixarene derivatives, calix[4]arene-crown ethers have attracted intense interest as alkalimetal-selective extractants [2332]. The ion selectivity of this class of compounds is controlled mainly by the conformation of the calixarene platform, the size of the crown ether ring and substituents attached with the calix or crown moiety (ies). Among various conformations of the calixarene, 1,3-alternate conformers have been studied extensively as complexing agent for alkali metal ions [2639]. Other conformers have also been prepared but metal ion complexation studies are rare. Among various crown ethers, crown-5 and crown-6 containing calixarene derivatives are found more suitable for complexation with alkalimetal ions [2232]. We also reported synthesis of a series of p-tert-butylcalix[4]arene-crown-5/6 with various substituents in lower rim and study on their competitive complexation property with selected alkali and alkaline earth metal ions [2932].

Corresponding author. Tel.: + 91 278 2567760; fax: + 91 278 2567562. E-mail address: ppaul@csmcri.org (P. Paul). 1387-7003/$ see front matter 2012 Elsevier B.V. All rights reserved. doi:10.1016/j.inoche.2012.05.028

In this communication, we report competitive complexation property of calix[4]arene-crown-n (n = 4, 5 and 6, Fig. 1) with the metal ions Li+, Na+, K +, Mg 2+, Ca2+ and Sr2+. Selectivity of these ionophores towards the above mentioned metal ions has been evaluated by twophase extraction using aqueous solution containing equimolar mixture of these ions. The concentration of metal ion in the extract (organic phase) has been estimated by ion chromatographic assay. Association constants for strongly interacting metal ions were also determined. The molecular structures of the Na+ and K + complexes of the two ionophores were also determined by single crystal X-ray study. The ionophores 13 were synthesized following the modied published procedures [29,30,40], route followed for the synthesis [Scheme S1, ESI] and details of the synthetic procedures [S2, ESI] are available as ESI. These compounds were characterized on the basis of elemental analysis, mass spectrometry, IR and 1H NMR data [S2, ESI]. Elemental analysis and mass data are in excellent agreement with the calculated values. It may be noted that the m/z values for 1 appeared as [1 + Na] +, whereas for 2 and 3, it appeared as both Na + and K + salt, [2/3 + Na] + and [2/3 + K] +, with different intensity of peaks. Association with different cations in ESI-MS depends on complexation ability of the ligand with various metal ions, and the variation in peak intensity depends on the stability of the complex formed. Ion-binding property of 13 towards alkali and alkaline earth metal ions was evaluated by two-phase extraction method using equimolar mixture of metal ions. The experiments were carried out with an aqueous solution containing equimolar amounts of Li +, Na +, K +, Mg 2+, Ca 2+ and Sr 2+ as their picrate salts and the respective ionophore dissolved in dichloromethane [29]. The metal ions

Please cite this article as: V. Ramakrishna, et al., Synthesis, crystal structures and competitive binding property of a family of functionalized calix[4]arene ionophores, Inorg. Chem. Commun. (2012), doi:10.1016/j.inoche.2012.05.028

V. Ramakrishna et al. / Inorganic Chemistry Communications xxx (2012) xxxxxx Table 1 Concentration of metal ions in the extract and selectivity ratio with respect to potassium ion. Compound Concentration (%) of metal ion in the extracta Li+ 2 Fig. 1. Structural drawings of the calix[4]arene-crown-n; n = 4 (1), 5 (2) and 6 (3). 3 Na+ K+ Mg2+ Ca2+ Sr2+ Selectivity ratiob K +/ Na+ K +/ Mg2+ 8.59 33.87 K+/ Ca2+ 5.41 15.85

Trace 34.42 49.81 4.49 amount Trace 32.09 59.57 2.16 amount

10.93 Trace 0.84 amount 6.03 Trace 1.08 amount

added with stoichiometric amount and also with 25, 50, 75 and 100 times excess with respect to the concentration of ionophore used [S3, ESI]. The organic phase containing the complex formed was separated and the metal ions in the extract were determined by ion chromatographic assay [S4, ESI]. It may be noted that the extract obtained from ionophore 1 exhibited only trace amount of a few metal ions, indicating poor complexing ability of this ionophore towards the metal ions tested. It was also examined with the aid of 1H NMR study, the spectra of 1 and that in presence of metal ions were recorded in CDCl3. The 1H NMR spectra recorded in presence of metal ions did not show any signicant change compared to that of 1, indicating that no considerable amount of complex is formed with the metal ions used for this study. This is probably due to cavity size of crown-4, which is not large enough to allow the entry of the hydrated metal ion for complex formation. The organic extracts of 2 and 3 showed the presence of Na+, K +, Mg2+ and Ca2+, and the distributions of metal ions in the extracts, together with values of the observed selectivity ratios, are shown in Table 1. The plot of the mole fraction of the metal ions extracted against concentration of metal ions used in the extraction process is shown in Fig. 2 for ionophore 3, similar plot for 2 is given as ESI (S5). The result clearly suggests that these two ionophores prefer to bind Na+ and K + over the other metal ions; Mg2+ and Ca 2+ also form considerable amount of complexes but Li+ and Sr2+ do not form any complex with these ionophores. Small size and high hydration enthalpy ( 520 and 1443 kJ mol 1 for Li+ and Sr2+, respectively) are likely the factors, which prevented this metal ion to form complex. For Sr2+, probably the large size of the hydrated metal ion also played important role to prevent its entry into the cavity of the ionophore to form complex. The other notable observation is that the selectivity ratio (K+/ Na+) for 2 towards K + and Na+ ions is 0.84 (Table 1), whereas the same for 3 is 1.08, indicating that the selectivity towards K + over Na + is signicantly high for 3, which is due to better size matching for K + with the crown-6 cavity. For structural elucidation of these complexes, we synthesized both Na+ and K + complexes of the ionophores 2 and 3. These complexes were synthesized by stirring the solution of Na+/ K + picrate and the ionophore in chloroformmethanol (5:1) at room temperature for 24 h and puried from dichloromethane [S6, ESI]. These complexes were characterized on the basis of elemental analysis,

a Concentration (%) of metal ion in the original solution (before extract), Li+ = 3.18, Na+ = 10.4, K+ = 17.7, Mg2+ = 10.9, Ca2+ = 18.1 and Sr2+ = 39.5. b The ratio is calculated by [% of K+ in the extract][% of Mn+ in the original solution]/ [% of Mn+ in the extract][% of K+ in the original solution].

mass spectrometry, IR and 1H NMR data and nally molecular structures were determined by single crystal X-ray study. It is interesting to note that the ESI-MS of all the four complexes exhibited m/z values corresponding to both Na + and K + complexes; however the peak with 100% intensity corresponds to the complex, which used is for measurement, i.e., for Na + complexes the 100% peak corresponds to [2/ 3.Na+] and for K+ complexes the 100% peak corresponds to [2/3.K +] [S6, ESI]. To check purity of the complexes, powder X-ray diffraction patterns of all the four complexes were recorded and these patterns were compared with those obtained by simulation from single crystal X-ray data, good matching of both the patterns (S7 and S8, ESI) suggests that the molecular structures determined from single crystal X-ray analysis (described below) represent the bulk complexes. Suitable crystals for X-ray study of these complexes were grown from THF-toluene (2:3), except K + complex of 3, which was grown from dichloromethanetoluene (1:1). The 1H NMR spectra of the ionophore 3 and that of its Na + and K + complexes (3.Na+.pic and 3.K +.pic) are shown in Fig. 3. It may be noted that in the 1H NMR spectra of the ionophore, a typical AB pattern was observed for the methylene bridge (ArCH2Ar) protons of the calix moiety, that is two widely separated doublets at = 3.904.65 and 3.123.36 ppm (J = 1213.8 Hz), which suggests that these ionophores exist in cone conformation in solution [29,41,42]. The low-eld doublet is due to axial hydrogen atom, and the high-eld doublet is due to equatorial hydrogen atoms of the methylene bridge. These doublets are also observed in the Na + and K + complexes with slight change in chemical shifts, indicating that the cone conformation of the calix moiety is retained in the complexes. The chemical shifts of the signals due to crown moiety ( = 3.714.15) changed signicantly upon complexation with metal ion (Fig. 3), indicating that the metal ion encapsulated in the crown cavity to form the complex. A few changes in chemical shifts are also noted in the aromatic

a
8
Fig. 2. Bar diagram showing the fraction of metal ions extracted from equimolar solution of Li+, Na+, K+, Mg2+, Ca2+ and Sr2+ at different concentrations of metal ions using the ionophore 3 (concentration of the ionophore was 0.002 M).

p pm

Fig. 3. 1H NMR spectra of the (a) ionophore 3, (b) complex 3.Na+Pic and (c) complex 3.K+Pic recorded in CDCl3.

Please cite this article as: V. Ramakrishna, et al., Synthesis, crystal structures and competitive binding property of a family of functionalized calix[4]arene ionophores, Inorg. Chem. Commun. (2012), doi:10.1016/j.inoche.2012.05.028

V. Ramakrishna et al. / Inorganic Chemistry Communications xxx (2012) xxxxxx

Fig. 4. Mercury diagram for the crystal structures of (a) 2.Na+.pic and (b) 2.K+.pic showing the labeling of coordinated atoms with the metal ions and the dimeric association in (b) (hydrogen atoms are omitted for clarity).

region ( = 6.677.06), which is due to overall conformational change of the molecule because of the complexation with metal ion. A new peak appeared at = 8.85 in the complexes due to picrate counter anion. The 1H NMR spectra of 2 and 3 are, therefore, consistent to the formation of complexes encapsulating metal ion in the calix-crown cavity. Molecular structures of the Na + and K + complexes of 2 (2.Na +.pic and 2.K +.pic) and 3 (3.Na +.pic and 3.K +.pic) were determined from single crystal X-ray study, and details of unit cells are available as ESI [S9]. Suitable crystals for X-ray study were grown from THF/ CH2Cl2-toluene, and the analysis of the data revealed the structures shown in Figs. 4 and 5 (hydrogen atoms and lattice solvent molecules are omitted for clarity). In all of these complexes, the metal ion is coordinated to one of the phenolic OH of the calix moiety and with oxygen atoms from picrate anion and crown moiety. The picrate anion is coordinated in a bidentate fashion using the oxygen atom of the deprotonated OH and one of the oxygen atoms of an adjacent nitro group. The Na + ion is six coordinated in 2.Na +.pic and seven coordinated in 3.Na +.pic, whereas K + is seven coordinated in 2.K +.pic and eight coordinated in the complex, 3.K +.pic. It is interesting to note that for Na +, two of the oxygen atoms of the crown moiety and for K +, one of the oxygen atoms of the crown ring do not participate in coordination. This is because of the size of the metal ions and this constrain, which the crown ring is expected to experience for coordination of all of the oxygen atoms to the same metal ion. The larger K+ ion is better tted in the cavity as evident from higher coordination number compared to Na+ in the same crown ring. For 3, due to more exibility of the larger crown ring (crown-6), more oxygen atoms could come closer to metal ion for coordination. It is noteworthy that the cone conformation of the calixarene moiety, found in the ionophore, is retained even after complexation with metal ion. The Na+.O and K+.O distances in both the complexes are found in the ranges 2.279(4) to 2.698(6) and 2.630 (3) to 2.938(4) , respectively. In all of these complexes, there are several intra- and intermolecular OHO and CHO interactions, in which picrate anion is also involved. In an attempt to understand the interaction between the 2.Na+.pic with lattice host p-xylene and 2.K+.pic with lattice host toluene, packing and hydrogen bonding interaction has been analyzed in detail (Table S1). Packing diagrams with hydrogen bonding between 2.Na+.pic and p-xylene viewed down b-axis, and the

Fig. 5. Mercury diagram for the crystal structures of (a) 3.Na+.pic and (b) 3.K+.pic showing the labeling of coordinated atoms with the metal ions (hydrogen atoms are omitted for clarity).

interaction between 2.K+.pic and toluene viewed down c-axis are given in supplementary data (S10 and S11). In the case of 2.K+.pic, the dimeric complex is involved in inter and intramolecular C-HO and OHO H-bonding generating a corrugated layer along ab plane. Lattice toluene guest molecules are located in the clefts of the corrugated layer and anchored by CH interaction between the phenyl hydrogen H9 of the calix ring with the centroid of the toluene guest with C1gH9 distance 3.21 . For the Na+.pic complex, host moiety is

Please cite this article as: V. Ramakrishna, et al., Synthesis, crystal structures and competitive binding property of a family of functionalized calix[4]arene ionophores, Inorg. Chem. Commun. (2012), doi:10.1016/j.inoche.2012.05.028

V. Ramakrishna et al. / Inorganic Chemistry Communications xxx (2012) xxxxxx

Table 2 Molar ratio of picrate to host in organic layer (R) and association constants (Ka) for 2 and 3 with Na+ and K+. Compound R Na+ 2 3 0.19 0.14 K+ 0.34 0.37 Na+ 1.47 10 9.6 104
5

K +. Molecular structures of the Na+ and K + complexes have been determined by single crystal X-ray study. This study reveals that the size-matching factor plays the predominant role in ion-selectivity. Acknowledgements

Ka K+ 2.6 10 4.9 106


6

oriented diagonal to ac-plane involving inter and intra molecular CH O and OHO interactions. Lattice p-xylene guest molecules are positioned between the diagonally oriented Na+.pic host and anchored by CHO interaction. Thus, the methyl hydrogen H43A and phenyl hydrogen H46 of the symmetrically disposed host is involved in a bifurcated CHO interaction with the nitro oxygen O13 of the picrate from the diagonally oriented Na+.pic host layers (C43H43AO13: H43A ..O13 = 2.40; C43O(13) = 3.233(13); b C43H43AO13 = 145 and C46H46.O13:H46....O13 = 2.59; C46....O13 = 3.310(10); C46 H46O13 = 134). Details of the hydrogen bonding interaction for both the complexes with symmetry code are given in supplementary data (Table S1). The association constants (Ka) for 2 and 3 with Na + and K + were determined by two phase extraction method following the published procedure [29,4345]. The association constants were determined using Eq. (1), where Ka is the association constant, Kd is the distribution constant, R is the molar ratio of picrate to host in the organic layer, [Gi]H2O is the initial concentration of the guest (metal ion/ picrate), [Hi]CHCl3 is the initial concentration of the host (ionophore) in chloroform,VCHCl3 the volume of the organic layer (chloroform) and VH2Othe volume of the aqueous layer. Ka R n  o2 1RK d Gi H2 o RH i CHCl3 V CHCl3 =V H2 o 1

We are grateful to the Department of Science and Technology (DST), Government of India, for nancial support. S.P. gratefully acknowledges the CSIR for awarding Senior Research Fellowship (SRF). We thank Dr. Babulal Rebary for assistance in recording ion chromatography, Mr. H. Bhatt and Dr. V. Boricha for recording NMR spectra, Mr. Arun K. Das for recording mass spectra and Mr. V. Vakani for elemental analysis. We thank CSIR, New Delhi for generous support towards infrastructures and core competency development. Appendix B. Supplementary data CCDC 834098, 834099, 834100 and 834101 contain the supplementary crystallographic data for 2.Na +.pic, 2.K +.pic, 3.Na +.pic and 3.K +. pic, respectively. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc. cam.ac.uk/data_request/cif. Other supplementary data associated with this article can be found in the online version. Supplementary data to this article can be found online at http://dx.doi.org/10.1016/ j.inoche.2012.05.028. References
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Details of the determination of different parameters of Eq. (1) are given as ESI [S12] and the association constant thus determined are given in Table 2. The data show that the association constant for K + is signicantly higher compared to that of Na+, which is due to strong complexing ability of the larger K + because of the better sizematching tting of the metal ion with the crown cavity, as evident from the crystal structures. For Na+, two of the oxygen atoms of the crown moiety are not involved in making interaction with metal ion, whereas for K+ only one oxygen atom is left out for making coordination for both the ionophores. It is also interesting to note that between two ionophores, Na + shows higher binding constant with crown-5 (2.Na+.pic) compared to that of crown-6 (3.Na +.pic), whereas K + exhibits reverse order. This suggests that Na+ being smaller ts better with the smaller cavity size of the crown-5 of ionophore 2 to make strong interaction and the larger K+ ion matched well with the cavity size of the crown-6 of 3 and forms strong complex. The data are consistent to the observation noted in the crystal structures of the complexes. In summary, a number of calix[4]arene crown ethers with hybrid calix-crown cavity of different size as ionophore have been synthesized in cone conformation to evaluate their performance as complexing agent towards Li+, Na +, K +, Ca2+, Mg2+ and Sr2+. Competitive complexation study in aqueous media with the mixture of cations taken shows preferential binding of K + and Na+ for the ionophores containing crown-5 and crown-6 as ion-binding cavity and the latter shows signicantly higher selectivity towards K +. Ca 2+ and Mg2+ also form complexes with 2 and 3 but with very poor selectivity, especially for 3. Li+ and Sr2+ do not exhibit any complex formation with these ionophores. No metal ion used in this study shows complexation with the ionophore 1. Association constants for 2 and 3 have been determined with Na + and K + and the values are signicantly higher for

Please cite this article as: V. Ramakrishna, et al., Synthesis, crystal structures and competitive binding property of a family of functionalized calix[4]arene ionophores, Inorg. Chem. Commun. (2012), doi:10.1016/j.inoche.2012.05.028

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Please cite this article as: V. Ramakrishna, et al., Synthesis, crystal structures and competitive binding property of a family of functionalized calix[4]arene ionophores, Inorg. Chem. Commun. (2012), doi:10.1016/j.inoche.2012.05.028