Consistent Binding Aptitude of Halides and ...

DOI: 10.1002/slct.201702840 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57

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z Organic & Supramolecular Chemistry

Consistent Binding Aptitude of Halides and Oxyanions via Cooperative vs. Non-Cooperative Binding Modes by Neutral Napthyl Bis-Urea Receptors Biswajit Nayak, Utsab Manna, and Gopal Das*[a] Two electron-rich napthyl ring containing bisurea receptor derived from ortho (L1) and meta (L2)-phenylenediamine moiety were designed and synthesized for investigating their anion coordination behavior. L1 self-assembled in presence of organic terephthalate anion into a dimeric pseudo-capsular hostassembly sealed by tetrabutylammonium counter cation (Complex 1 c). However, L2 self-assembled in 2:4 host-guest fashions (Complex 2 d) with H-bonded dihydrogenphosphate tetrameric anionic guest in the presence of excess n-TBA (H2PO4). Further,

Introduction Within the arena of comprehensive area of supramolecular chemistry, anion coordination by hydrogen bonding scaffolds has emerged into noticeable and active field of research.[1] The importance of supramolecular chemistry of anions derives strength from its invaluable role in a range of environmental, biological and medical fields. Its prominence in living organisms and its impact on protein binding by molecular receptors is also well known.[2–5] Researchers get motivated to develop neutral receptors having hydrogen bonds handy by specific binding sites from amide,[6] urea,[7] pyrrole,[8] and indole[9] functionalities for binding of anionic guests, by the fact that in natural system protein can efficiently and selectively bind anions by non-covalent interactions. Encapsulation of chloride inside the cavity diammonium receptor was first reported by Park and Simmons in the year 1967, which were essentially first anion complexes.[10] The idea of anion coordination, on the basis of the exploration of cyclic ammonium host with halide ions, was first suggested by Lehn in the year 1978.[11] In recent years, this field has grabbed much more attention and it is well known that anion complexes show double valance as transition metal complex where anions behave as the “primary valence” while “secondary valence is satisfied by hydrogen bonds between the receptor and anion which provide a “coordination number.[12] In this context, the design [a] B. Nayak, U. Manna, Prof. G. Das Department of Chemistry Indian Institute of Technology Guwahati Assam 781039, India Tel: + 91-361-2582313 Fax: + 91-361-2582349 E-mail: [email protected] Supporting information for this article is available on the WWW under https://doi.org/10.1002/slct.201702840

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receptor L1 has been found to self-assembled into unimolecular cooperative 1:1 complex in presence of spherical Chloride anion (Complex 1 a) and planar Acetate anion (Complex 1 b). Moreover, receptor L2 forms similar kind of non-capsular hostguest assembly in presence of spherical halides like Cl , Br , and F . To validate the result obtained in the solid state studies, 1 H-NMR titration experiments have also been performed using n-TBA salts of anions to inspect the solution state anion binding behavior of isomeric receptors L1 and L2. of prospective ligands are based on the rationale of attainment of overall coordination saturation of anions. Hence the design of suitable and potential three-dimensional polymeric receptor is vital for full entrapment or encapsulation of relatively larger oxyanions. Tripodal receptor having structurally flexible preorganized cavity with urea functionalization is a renowned area for anion binding and recognition.[13] Thus in the realm of supramolecular chemistry, synthetic design of a ligand accomplished of strong biding towards anions of different dimensionality (spherical, tetrahedral, planar) is an area of immense interest.[14–16] To facilitate the binding of anion, most of the commonly reported urea functionalized scaffolds consists of electron withdrawing group making the receptor more electron deficient in nature.[17] Hence, in contrast our challenge is to design and syntheses of urea functionalized receptor consisting electron rich moiety. Among several oxyanions, recognition of tetrahedral oxyanions, mainly sulphate and phosphate via entrapment within the suitable neutral organic receptor has been the focus of special research interest, especially in sulphate and phosphate binding proteins[18–19] because of their roles in biological and physiological processes.[20–23] Reliant on its Immediate environment, H2PO4 is most abundant among all of the Inorganic phosphate that exists in three different forms, that are H2PO4 , H2PO4 and PO43 . In cluster chemistry self-complementary hydrogen bonding among H2PO4 anions underneath certain circumstances generate self-aggregated anion assemblies, known as “anion clusters” in solid state. Similar to water molecules H2PO4 anion shows both H-bond donor and acceptor properties. Well-defined oligomeric structures of H2PO4 anions containing cyclic dimers,[24,25] trimers,[26] tetramers,[27,28] hexamers,[29] and octamers[30] are known in the literature and have overwhelming structural similarities to different cyclic “water clusters”.[31–35] 3548

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Table 1. Key observation of size dependent diverse anion binding behaviors of the receptors. Anions with size

Neutral receptor-anion Complexes

Observation

Spherical Chloride (Cl ), Bromide (Br ), Fluoride (F )

1) Cooperative 1:1 host-guest assembly of L1-Cl 2) Non-cooperative 1.5:2 host-guest assembly of L2-Cl, L2-Br and L2-F. Cooperative monomeric 1:1 hostguest assembly of L1-OAc Terephthalate pseudo encapsulation of L1 in 2:4 host-guest fashion n-TBA Cation sealed 2:4 host-guest self-assembly of L2- H2PO4.

Anion recognition is solely affected by the cooperative binding of urea NH groups of ortho- isomer (L1) irrespective of nature of the anion. However the geometry and orientations of a particular receptor unit is consistently affected by the size and dimensions of the anions in case of meta-isomer L2.

Planar Acetate (OCOCH3 ) Planar Terephthalate Tetrahedral phosphate (H2PO4 )

We have shown the self-association of H2PO4 into a cyclic decameric (H2PO4 )10 cluster stabilized by a tripodal polyammonium receptor[36] and self-assembly of a tris(Urea) receptor as tetrahedral cage for the encapsulation of a discrete tetrameric mixed phosphate cluster(H2PO4 *HPO42 )2.[37] There are quite a few structural proofs of monotopic recognition of phosphate inside acyclic and macrocyclic systems.[38,39] In our on-going effort to strategy the host for encapsulation of hydrated and/or solvated anion cluster,[40–42] herein we structurally validate a n-TBA cation sealed terephthalate dianion

ality either in cooperative syn-fashion or in non-cooperative anti-mode of urea groups, so thus having various interacting possibilities depending upon the guests as well as positional aromatic functionalization of hosts. X-ray analyses of receptoranion complexes have given the detailed structural information which demonstrates the divergences of binding with particular receptor with the particular anion. Traditionally, crystallisation has been the main focus in anion-recognition chemistry to understand the structural insight of receptor-anion. Single crystal XRD investigation of receptor-anion neutral complexes and selective binding behaviour of receptors towards halides and oxyanions of various dimensionalities depending upon the ortho and meta- phenylene based isomeric receptors and the size of anions are tabulated and presented in Table 1 and Figures 1–4 respectively. Cooperative vs. non-cooperative binding of spherical halides: Structural diversity in chloride complexes

Scheme 1. Synthetic scheme of receptors L1 and L2.

host guest assembly (1 c) inside the dimeric host cavity of ortho-phenylene based receptor L1, whereas its isomeric meta receptor L2 forms 2:4 cooperative cyclic tetrameric dihydrogen phosphate complex (2 d).

Results and Discussion Design aspects of anion binding receptors The ortho and meta-phenylenediamine based two isomeric bisurea receptors L1 and L2 were synthesized in high yield by the reaction of respective one equivalent of o-phenylenediamine and m-phenylenediamine with two equivalents of 1-napthyl isocyanate in acetonitrile medium (Scheme 1). A suitable synthetic receptor should possess a particular rigid or flexible supramolecular architecture to bind with anions of different sizes. Dipodal receptors L1 and L2 both hold their rigid construction keeping the adjacent urea moieties of two aromatic pods which can receive guests of varied dimensionChemistrySelect 2018, 3, 3548 – 3554

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Structural elucidation of complex 1 a [(L1.TBACl)] revealed the unimolecular self-assembly of L1 in presence of spherical chloride guest assemblage within its complementary cavity (Figure 1a) suitably sealed by two n-TBA cations (Figure. 1 b). Xray analysis exposes the occurrence of cis-orientation adjacent urea -NH moieties of particular receptor which help in the 1:1 host-guest assembly formation by cooperative H-bonding interactions of urea N H group and chloride ion through four N–H···Cl interactions. Additionally, the non-capsular assembly of chloride and L1 receptors are stabilized by two C H···O, C H···Cl and two weak C H···p supportive interactions between the two exterior n-TBA units with chloride and receptor, respectively (Figure S26b, Supporting Information). From asymmetric unit it has been observed that the stoichiometry of the complex 2 a is 1:1.5. In presence of excess chloride ions in DMSO isomeric receptor L2 forms 1.5:2 host-guest complexations via different number of H-bond sharing of non-cooperative urea groups from two symmetrically identical receptor units. Structural elucidation reveals that in complex 2 a, two symmetrically independent chloride anions accept six strong N H···Cl bonds [2 for Cl1 and 4 for Cl2] among which four H-bonds are donated from one receptor unit and rest are donated by the urea groups of other identical receptor unit of the non-capsular 1.5:2 assembly (Figure 1c). The stability of L2-chloride complex 3549


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Figure 1. X-ray structure of complex 1 a and 2 a (partial) depicting (a) hydrogen bonding contacts of the chloride with receptor L1 and n-TBA cations, (b) entrapment of the guest inside dimeric barrel (space-fill), (c) hydrogen bonding contacts of the chloride with receptor L2, (d) spacefill view of receptor L2 with chloride.

Figure 2. Molecular packing of (a) complex 1 b (wave like) and (b) complex 1 c (staircase) viewed along crystallographic b-axis.

is strengthened by three C H··· p and three C H···O interactions of receptors and n-TBA counter-cations (Figure S26a, Supporting Information). In case of ortho substituted ligand all the N H groups of the both the arms are pointed inward and converged towards the same chloride anion. However in meta substituted ligand, N H groups of both the arms of the dipodal ligand are pointed in the opposite direction and bind two different chloride ions simultaneously. Thus, each arm of complex 2 a is more planar in comparison to complex 1 a (torsional angle between the naphthalene ring and the urea NH is ~ 1718 in

complex 1 a and ~ 1758 in case of complex 2 a respectively). This is also reflected in the relative bond distances of both the complexes. Stronger binding is observed in complex 2 a ˚ and 2.333 A˚) in compar(N H···Cl bond distances are 2.478 A ison to complex 1 a (N H···Cl bond distances are 2.609 A˚ and 2.511 A˚). The divergence of binding of two isomeric receptors L1 and L2 in solid state towards chloride anion is probably ascribed due to the isomeric variation of ortho and metadiamine, the urea groups of receptor L1 orients in closer proximity helping in cooperative chloride binding, while in contrary, receptor L2 exhibits non-cooperative halide binding of urea groups possibly because of larger distance among the urea groups of a particular receptor moiety as well as less coordination number of halides as observed from solid state study. Two symmetrically distinct bromide ion is coordinated by two symmetrically identical L2 receptor (complex 2 b) via six strong N–H···Br and three C–H···Br interactions (Figure S29, Supporting Information) conforming 1.5:2 non-capsular hostguest assembly similar to the chloride complex. However, larger bromide anion forms relatively weaker complex (N H···Br bond ˚ and 2.471 A˚). Two urea groups from one distances are 2.664 A ligand bind one bromide ion, while the one urea groups of

Figure 3. X-ray structure of complex 1 b and 1 c (partial) depicting (a hydrogen bonding contacts of the acetate with receptor L1 and n-TBA cations, (b) entrapment of the guest inside dimeric cavity (space-fill), (c) interaction of anion with ligand and n-TBA cation (d) space fill view of receptor L1 with terephthalate.


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Figure 4. X-ray structure of complex 2d (partial) depicting (a) hydrogen bonding contacts of the phosphate with receptor L2 and n-TBA cations, (b) space fill model of (2 + 4) host-guest assembly, (c) molecular packing of complex 7 a viewed down the crystallographic b-axis, (d) interaction of symmetrically distinct monovalent phosphates with one another to form cyclic tetramer.

other ligand chelate another bromide ion. The non-capsular assembly of bromide and L2 receptors are stabilized by three C H···O and two weak C H···p supportive interactions between the two exterior n-TBA and receptors. Similarly the crystal structure of fluoride complex 2 c clearly shows that out of two symmetrically distinct fluoride ions, F1 and F2 are coordinated via three and six H-bonds respectively, conforming non-capsular host-guest assembly similar to Cl and Br complex (Figure S30, Supporting Information). Moreover, complex 2 c is stabilized by one C H···O and one weak C H···p supportive interactions between the two external n-TBA and receptors. In this case distance between urea NH and guest is 1.954 A0 and 1.880 A0 which is shorter than bromide complex because size of fluoride is much smaller than bromide ion. Structural discrepancy in cooperative acetate and terephthalate complex: Cation sealed complex The acetate complex 1 b of L1 forms 1:1 host-guest assembly via cooperative H-bonding interactions of urea N H group with acetate ion (Figure 3a) through four N–H···O interactions via formation of one dimensional coordination polymer like structure (Figure S28, Supporting Information). The receptoracetate self-assembly is also stabilized by seven C H···O and one weak C H···p supportive interactions between the two peripheral n-TBA units with respective acetate and receptor. DMF solvated 2:1 host-guest complex 1 c forms in presence of organic terephthalate ion which is coordinated by two symmetrically identical L1 receptor units and four n-TBA cations via eight strong N–H···O and six C–H···O interactions conforming 2:1 (Figure 3c) pseudo-capsular cation-sealed host-guest assemChemistrySelect 2018, 3, 3548 – 3554

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bly. Each carboxylate group of a terephthalate dianion is coordinated to a receptor molecule by four N H···O hydrogen bonds to the two urea functions. Two identical-symmetric receptor molecules are flipped inward towards each other in face to face fashion and so generate a pseudo molecular capsule engulfing a terephthalate dianion. The packing motif of acetate complex forms a wave like structure (Figure 2a) whereas complex 1 c forms a stair case like packing structure (Figure 2b). Additionally, complex 1 c is also stabilised by intermolecular p stacking and C–H···O interaction with adjacent receptor moieties. In complex 1 b the orientation of naphthalene ring is out of plane with respect to the central benzene ring; whereas in case of complex 1 c it is in plane with respect to the central benzene ring. The angle between the two planes bisecting the napthyl ring in both the complexes are different. Both urea NH and central benzene ring of receptor L1 in presence of two different anions was found to be 62.058 in case of complex 1 b where as in complex 1 c it was about 71.968. Comparative structural analysis of complex 1 b and 1 c of respective planar acetate and terephthalate of receptor L1 demonstrates the non-capsular 1:1 host-guest assembly of acetate ion by cooperative binding of urea groups (Figure 3a) whereas, terephthalate anions are pseudo-encapsulated into the dimeric cavity L1 receptor in 2:1 host-guest fashion (Figure 3c) which may be attributed to the large size of organic terephthalate dianion compared to smaller inorganic acetate anion. Cooperative cation sealed phosphate tetramer The dihydrogen phosphate cluster complex 2 d contains symmetry-independent two receptor molecules, four phosphate anions, and four n-TBA cations (Figure 4a). The presence of four n-TBA cations indicated the only possible combination of monovalent dihydrogen phosphate. Interestingly four symmetrically distinct monovalent phosphates interact with one another to form cyclic tetramer (Figure 4a, 4 d). The crystal structure clearly shows that four independent phosphate ions are coordinated by two symmetrically distinct L2 receptor units via eight strong N–H···O and four ortho-aryl C– H···O interactions (Figure 4a) constructing 2:4 host-guest assembly. Cyclic tetrameric dihydrogen phosphate cluster is fully sealed by four pair of symmetrically distinct n-TBA cations. The host-guest tetrameric cluster assembly of monovalent dihydrogen phosphate and L2 receptors is stabilized by additional seven C H···O and five weak C H···p supportive interactions from the exterior n-TBA units. Density functional theory (DFT) studies of the receptors Being unable to grow good quality crystals of the free receptors L1 and L2, we have performed density functional theory (DFT) studies for structural elucidation of them. This study reveals the trans orientation of first urea NH adjacent to central aromatic ring in case of free receptor L1, whereas the cis orientation of first urea NH adjacent to central aromatic ring 3551


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has been observed in free ligand structure of L2 (Figure 5a, 5 b). DFT optimizations of the receptors were carried out with the

Figure 6. Partial quantitative acetate titration spectra (600 MHz, DMSO-d6) of) L1 with the observable shifts of urea –NH resonance upon the addition of 1 equivalent of n-TBACH3COO.

Figure 5. Molecular architecture of the receptors and optimized geometry of the free receptors (a) L1, (b) L2 using B3LYP/6-31 + G(d,p) basis set.

B3LYP/6-31 + G (d,p) basis set. A correlation of N–H···A angle vs. N–H···A distance shows that all the receptor N–H H-bonding interactions with corresponding anion in solid state are in the strong H-bonding region of d (H···A) 2.5 A˚ and d (D···A) 3.2 A˚ (Table S1 Supporting Information). The scattered plot of N–H···A angles vs. H···A distances (Figure S31, Supporting Information) of individual anion complexes also demonstrates that most of the non-covalent interactions exhibiting strong Hbonding character. Crystal parameters and refinement data of all the anion complexes of receptor L1 and L2 are tabulated in Table S2. (Supporting Information) Solution-State study by NMR Spectroscopy The solution-state anion binding properties of L1 and L2 were studied by qualitative as well as quantitative 1H NMR experiments in DMSO-d6 using the quaternary ammonium (n-TBA) salt of the AcO , H2PO4 and F as established from the solid state. Comparative partial 1H-NMR stack plots of L1 with increasing concentration of n-TBACH3COO showed huge downfield shift of NHa and NHb and relatively less shift of o-aryl CH protons (Figure 6) of receptor L1 due to the formation of receptor-anion complex in solution state. The acetate complex (1 b) showed an average downfield shift of ~ 1.353 ppm and ~ 1.125 ppm of –NH protons respectively (Figure 6). However, complex 1 c showed an average downfield shift of ~ 0.691 ppm and ~ 0.333 ppm (Figures S13, Supporting Information) in solid state. Afterward, the fluoride complex (2 c) and phosphate complex (2 d) revealed an average downfield shift of 1.945 and 2.054 –NH protons for complex 2c and a shift of 1.955 and 2.02 ppm for complex 2d respectively (Figures S21, S23, Supporting Information), while the 1H- NMR titration of L1 and L2 upon gradual addition of respective n-TBAF and n-TBAH2PO4, a huge average shift of of respective 2.512 and ChemistrySelect 2018, 3, 3548 – 3554

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1.926 ppm for fluoride complex and 1.923 and 1.527 ppm for H2PO4 complex –NH protons were observed (Figure 7a and 7 b). In case of titration spectra of complex (2 d) here we observed a huge downfield shift of –NHa protons than that of NHb protons, proofs that the H2PO4 binds strongly with NHa protons and also witnessed an average downfield shift of ortho aryl C H proton, which validate the solid state binding. A Job’s plot investigation of titration data gave a mixed equilibrium between 1:3 and 1:2 host-guest stoichiometry of L1 with aliquots of standard n-TBACH3COO solution (Figures S32, Supporting Information). On the other hand, 1H NMR titration data of L2 with aliquots of standard n-TBAF solution resulted a mixed equilibrium between 1:2 and 1:1 host and guest (Figure S33, Supporting Information) which is common in literature and titration data of L2 with aliquots of standard nTBAH2PO4 provided the mixed stoichiometry 2:1 and 1:1 equilibrium between host and guest (Figure S34, Supporting Information) from Job’s plot. The discrepancy in binding of anions in solid and solution states is common. Here, the alteration of binding of one or two fluoride ions in solution state against one chloride ion in solid state possibly attributed to the more systematized and rigid receptor arrangement in solid compared to more loose and loose orientations in solution. The presence of hydrogen bonded anions in all the complexes of L1 and L2 have also been confirmed by FT-IR analysis. More or less, significant shift (54-60 cm 1) in the stretching frequency of urea –NH in the complexes compared to free receptors further backings the existence of strong N– H···A hydrogen bonds between host and guest (Supporting Information).

Conclusion In summary, we have established the effect of positional isomerism in a set of electron donating 1-napthyl functionalized bis-urea receptors in solid as well as solution-state anion 3552


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Figure 7. Comparison between the expanded partial 1H NMR spectra of L2 upon titration with (a) n-TBAF and (b) n-TBAH2PO4 in DMSO-d6.

binding of different extents. Structural interpretation revealed that the ortho-phenylene based receptor L1 has the capability to self-assemble with spherical halide as well as planar organic and inorganic oxyanions in diverse stoichiometries. However, meta-phenylene based receptor L2 has the ability to cooperative trapping of monovalent inorganic H2PO4 . In contrary, spherical halides (Cl , Br and F ) self-assembles with the L2 receptor in an identical non-cooperative fashion may be due to the less coordination number of halides compared to oxyanions. Thus the report of well-organized unparalleled terephthalate dianion complex and cyclic tetrameric H2PO4 complex within the dimeric core of neutral organic receptor L1 and L2 irrespectively, provides an excellent case of understanding the significance of supramolecular neutral host-guest assembly. Supporting Information Summary Synthesis and characterization data for the receptor L1, L2 and their complexes 1 a, 1 b, 1 c, 2 a, 2 b, 2 c, 2 d; IR spectra, 13C NMR and 1H NMR spectra, figures, table, and, 1H NMR titration stack plots, job’s plot for solution state NMR, distance vs. angle plots, crystallographic refinement data, hydrogen-bonding data.

Acknowledgments This work was supported by CSIR and SERB through grant 01/ 2727/13/EMR-II and SR/S1/OC-62/2011, New Delhi, India. CIF IIT Guwahati and DST-FIST for providing instrument facilities. B.N. and U.M thank IIT Guwahati for fellowship.

Conflict of Interest The authors declare no conflict of interest.


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Keywords: cation shield complex · cooperative and noncooperative binding · dihydrogenphosphate cyclic tetramer complex · host-guest assembly · simple bisurea receptor

[1] J. L. Sessler, P. A. Gale, W. S. Cho, Anion receptor chemistry (Monographs in Supramolecular Chemistry), ed. Stoddart, J. F. RSC, Cambridge. 2006, 1–413. [2] a) K. Bowman-James, Alfred Werner revisited: Acc. Chem. Res. 2005, 38, 671–678; b) C. Caltagirone, P. A. Gale, Chem. Soc. Rev. 2009, 38, 520; c) J. L. Sessler, P. A. Gale, W. S. Cho, In Anion Receptor Chemistry: Monographs in Supramolecular Chemistry, J. F. Stoddart, Ed. Royal Society of Chemistry., Cambridge, 2006; d) Themed issue: Supramolecular chemistry of anionic species. Chem. Soc. Rev. 2010, 39, 3581; e) S. J. Brooks, S. E. Garcia-Garrido, M. E. Light, P. A. Cole, P. A. Gale, Chem. Eur. J. 2007, 13, 3320; f) S. J. Brooks, P. A. Gale, M. E. Light, Chem. Commun. 2006, 4344; g) P. R. Edwards, J. R. Hiscock, P. A. Gale, M. E. Light, Org. Biomol. Chem. 2010, 8, 100. [3] J. J. He, F. A. Quiocho, Science. 1991, 251, 1479–1481. [4] P. de Silva, H. Q. N. Gunaratne, T. Gunnlaugsson, A. J. M. Huxley, C. P. McCoy, J. T. Rademacher, T. E. Rice, Chem. Rev. 1997, 97, 1515–1566. [5] F. P. Schmidtchen, M. Berger, Chem. Rev. 1997, 97, 1609–1646. [6] a) S. O. Kang, R. A. Begum, K. Bowman-James, Angew. Chem., Int. Ed. 2006, 45, 7882; b) S. O. Kang, M. A. Hossain, K. Bowman-James, Coord. Chem. Rev. 2006, 250, 3038. [7] a) A.-F. Li, J.-H. Wang, F. Wang, Y.-B. Jiang, Chem. Soc. Rev. 2010, 39, 3729; b) V. Amendola, L. Fabbrizzi, L. Mosca, Chem. Soc. Rev. 2010, 39, 3889. [8] a) J. Yoo, M. Kim, S. Hong, J. L. Sessler, C. Lee, J. Org. Chem. 2009, 74, 1065; b) J. L. Sessler, J. Cai, H. Gong, X. Yang, J. F. Arambula, B. P. Hay, J. Am. Chem. Soc. 2010, 132, 14058. [9] a) P. A. Gale, Chem. Commun. 2008, 4525; b) J. L. Sessler, D.-G. Cho, V. Lynch, J. Am. Chem. Soc. 2006, 128, 16518; c) P. A. Gale, J. R. Hiscock, C. Z. Jie, M. B. Hursthouse, M. E. Light, Chem. Sci. 2010, 215. [10] a) J. W. Steed, J. L. Atwood, Supramolecular Chemistry. John Wiley & Sons, Ltd.: New York., 2009; b) J. L. Sessler, P. A. Gale, W.-S. Cho, Royal Society of Chemistry, Cambridge, U. K. 2006; c) P. A. Gale, Acc.Che. Res. 2006, 39, 465 475; d) P. A. Gale, S. E. Garca-Garrido, J. Garric, Chem. Soc. Rev. 2008, 37, 151–190; e) J. W. Steed, Chem. Soc. Rev. 2009, 38, 506– 519; f) P. A. Gale, Chem. Soc. Rev. 2010, 39, 3746–3771. [11] a) J.-M. Lehn, Acc. Chem. Res 1978, 11, 49–57; b) J. M. Lehn, Pure Appl. Chem 1978, 50, 871–892. [12] a) J. L. Atwood, J. W. Steed, Supramolecular chemistry of anions;VCH: Weinheim, 1997; b) K. Bowman-James, Acc. Chem. Res. 2005, 38, 671– 678; c) S. O. Kang, R. A. Begum, K. Bowman-James, Angew. Chem., Int. Ed. 2006, 45, 7882–7894; d) K. Bowman-James, A. Bianchi, E. Garca-EspaÇa, Anion Coordination Chemistry WileyVCH: Weinheim., 2011.

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[13] a) Jia, C. B. Wu, S. Li, X. Huang, Q. Zhao, Q.-S. Li, X.– J. Yang, Angew. Chem., Int. Ed. 2011, 50, 486; b) D. A. Jose, D. K. Kumar, B. Ganguly, A. Das, inorg. Chem. 2007, 46, 5817. [14] P. D. Beer, P. A. Gale, Angew. Chem., Int. Ed. 2001, 40, 486–516. [15] P. A. Gale, N. Busschaert, C. J. E. Haynes, L. E. Karagiannidis, I. L. Kirby, Chem. Soc. Rev. 2014, 43, 205–241. [16] M. E. Khansari, C. R. Johnson, I. Basaran, A. Nafis, J. Wang, J. Leszczynski, M. A. Hossain, RSC Adv. 2015, 5, 17606–17614. [17] Rui. Li, Yanxia. Zhao, Shaoguang. Li, Yang, Peiju.; Huang. Xiaojuan, XiaoJuan. Yang, Biao Wu, Inorg. Chem. 2013, 52, 5851–5860. [18] Z. Wang, H. Luecke, N. Yao, F. A. Quiocho, Nat. Struct. Biol. 1997, 4, 519. [19] J. W. Pflugrath, A. Quiocho, Nature. 1985, 314, 257. [20] B. Alberts, D. Bray, J. Lewis, M. Raff, K. Roberts, J. D. Watson, Molecular biology of the cell, 2nd ed.; garland press: new york,1990. [21] R. S. Kaplan, J. Membr. Biol. 2001, 179, 165. [22] B. Moss, Chem. Ind. 1996, 407. [23] C. Glidewell, Chem. Br. 1990, 26, 137. [24] R. Evans, J. A. K. Howard, J. S. O. Evans, Cryst. Growth Des. 2008, 8, 1635. [25] N. A. C. Baker, N. McGaughey, C. N. Fletcher, A. V. Chernikov, P. N. Horton, M. Hursthouse, Dalton Trans 2009, 965. [26] Y. Li, L. Jiang, X. L. Feng, T. B. Lu, Cryst. Growth Des. 2008, 8, 3689. [27] V. Blazek, K. Molcanov, K. Majerski-Mlinaric, B. Kojic-Prodic, N. Basaric, Tetrahedron. 2013, 69, 517. [28] A. Rajbanshi, S. Wan, R. Custelcean, Cryst. Growth Des. 2013, 13, 2233. [29] M. A. Hossain, M. Isiklan, A. Pramanik, M. A. Saeed, F. R. Fronczek, Cryst. Growth Des. 2012, 12, 567. [30] K. Raghuraman, K. K. Katti, L. J. Barbour, N. Pillarsetty, B C. L. arnes, K. V. Katti, J. Am. Chem. Soc. 2003, 125, 6955. [31] S. Pal, N. B. Sankaran, A. Samanta, Angew. Chem., Int. Ed. 2003, 42, 1741. [32] B.-Q. Ma, H.-L. Sun, S. Gao, Angew. Chem., Int. Ed. 2004, 43, 1374.


Wiley VCH 1812 / 109208

[33] R. Custelcean, C. Afloroaei, M. Vlassa, M. Polverejan, Angew. Chem., Int. Ed. 2000, 39, 3094. [34] C. Janiak, T. G. Scharmann, J. Am. Chem. Soc. 2002, 124, 14010. [35] P. S. Lakshminarayanan, E. Suresh, P. Ghosh, J. Am. Chem. Soc. 2005, 127, 13132. [36] M. N. Hoque, G. Das, Cryst. Growth Des. 2014, 14, 2962. [37] R. Chutia, S. K. Dey, G. Das, Cryst. Growth Des. 2015, 15(10), 4993–5001. [38] R. Dutta, P. Ghosh, Chem. Commun. 2014, 50, 10538. [39] C. Bazzicalupi, A. Bencini, V. Lippolis, Chem. Soc. Rev. 2010, 39, 3709. [40] a) U. Manna, B. Nayak, G. Das, Cryst. Growth Des. 2016, 16, 7163 7174; b) Md. N. Hoque, A. Basu, G. Das, Cryst. Growth Des. 2014, 14, 6–10; c) Md. N. Hoque, U. Manna, G. Das, Polyhedron 2016, 119, 307–316; d) R. Chutia, S. K. Dey, G. Das, Cryst. Growth Des. 2015, 15, 4993–5001. [41] a) U. Manna, R. Chutia, G. Das, Cryst. Growth Des. 2016, 16, 2893 2903; b) Md. N. Hoque, G. Das, Cryst Eng Comm. 2014, 16, 4447–4458; c) Md. N. Hoque, A. Basu, G. Das, Supramol. Chem. 2014, 26, 392–402. [42] a) U. Manna, S. Kayal, S. Samanta, G. Das, Dalton Trans. 2017, 46, 10374– 10386; b) Md. N Hoque, A. Basu, G. Das, Cryst. Growth. Des. 2012, 12, 2153–2157; c) A. Basu, G. Das, Chem. Commun. 2013, 49, 3997–3999. [43] G. M. Sheldrick, SAINT and XPREP, 5.1 ed.; Siemens Industrial Automation Inc.: Madison, WI, 1995. [44] G. M. Sheldrick, SADABS, empirical absorption Correction Program; University of Gçttingen: Gçttingen, Germany, 1997. [45] G. M. Sheldrick, Acta Crystallogr., Struct. Chem. 2015, 71, 3–8. [46] Mercury 2.3 Supplied with Cambridge Structural Database; CCDC: Cambridge, U. K., 20011.

Submitted: November 24, 2017 Revised: March 14, 2018 Accepted: March 15, 2018

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