Abstract
An E-4-styrylpyridine derivative endowed with 18-crown-6 as a substituent (E-1) was prepared and evaluated in acetonitrile as a potential ditopic ligand for protonated amino acids. The interactions of E-1 with the protonated amino acid perchlorates, ClO4− H3N+(CH2)nCOOH (n = 2, 5 and 10, A2, A5 and A10, respectively), were studied by optical methods, 1H NMR and mass spectroscopy. Complex formation involves coordination of the ammonium ion at the crown ether moiety of E-1. The spectral changes were evaluated by comparison with results obtained on protonation of E-1 with HClO4 and on association with ammonium perchlorate. Protonation by the protonated amino acid perchlorates was thwarted due to reversal of carboxyl/pyridinium pKA order in acetonitrile relative to water. Evidence for ditopic hydrogen bonding complex formation was especially sought for A10 because its CH2 chain is sufficiently long to bridge the distance between the crown ether and pyridyl N sites of E-1. Despite some subtle hints to the contrary, the absence of NOE interaction between the pyridyl protons of E-1 and the methylene protons of A10 indicates that the E-1•A10 complex is in the main monotopic, as is the case for A2 and A5. The photophysical and photochemical behaviour of the complexes change significantly on protonation by HClO4. The optical response of E-1 on binding the amino acids as ammonium salts allows convenient monitoring of complex formation.
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R. M. Izatt, N. E. Izatt, B. E. Rossiter and J. J. Christensen, Cyclic polyether-protonated organic amine binding: significance in enzymatic and ion transport processes, Science, 1978, 199, 994–996.
J. M. Lehn, Macrocyclic receptor molecules: aspects of chemical reactivity. Investigations into molecular catalysis and transport processes, Pure Appl. Chem., 1979, 51, 979–997.
A. Metzger, K. Gloe, H. Stephan and F. P. Schmidtchen, Molecular recognition and phase transfer of underivatized amino acids by a foldable artifical host, J. Org. Chem., 1996, 61, 2051–2055.
V. Thanabal and V. Krishnan, Porphyrins with multiple crown ether voids: novel systems for cation complexation studies, J. Am. Chem. Soc., 1982, 104, 3643–3650.
Y. Wu, H. An, J. Tao, J. S. Bradshaw and R. M. Izatt, Studies on the complexes of 4’-substituted benzo-15-crown-5 ligands with sodium picrate and picric acid, J. Inclusion Phenom. Mol. Recognit. Chem., 1990, 9, 267–274.
X. X. Zhang, J. S. Bradshaw and R. M. Izatt, Enantiomeric recognition of amine compounds by chiral macrocyclic receptors, Chem. Rev., 1997, 97, 3313–3361.
K. Tsubaki, K. Tanaka, T. Furuta, T. Kinoshita and K. Fuji, Recognition of the chain length of α,ω-diamines by a meso-ternaphtalene derivative with two crown ethers, Tetrahedron Lett., 2000, 41, 6089–6093.
I. Suzuki, K. Obata, J. Anzai, H. Ikeda and A. Ueno, Crown-ether-tethered cyclodextrins: superiority of the secondary-hydroxy side modification in binding tryptophan, J. Chem. Soc., Perkin Trans. 2, 2000, 1705–1710.
E. Bang, L.-W. Jung, W. Lee, D. W. Lee and E. Lee, Chiral recognition of (18-crown-6)-tetracarboxylic acid as a chiral selector determined by NMR spectroscopy, J. Chem. Soc., Perkin Trans. 2, 2001, 1685–1692.
P. D. Beer and P. A. Gale, Anion recognition and sensing: the state of the art and future perspectives, Angew. Chem., Int. Ed., 2001, 40, 486–516.
O. P. Kryatova, A. G. Kolchinski and E. V. Rybak-Akimova, Metal-containing ditopic receptors for molecular recognition of diammonium cations, Tetrahedron, 2003, 59, 231–239.
P. R. Ashton, I. Baxter, S. J. Cantrill, M. C. T. Fyfe, P. T. Glink, J. F. Stoddart, A. J. P. White and D. J. Williams, Supramolecular daisy chains, Angew. Chem., Int. Ed., 1998, 37, 1294–1297.
S. J. Cantrill, G. J. Youn, J. F. Stoddart and D. J. Williams, Supramolec-ular daisy chains, J. Org. Chem., 2001, 66, 6857–6872.
H. W. Gibson, N. Yamaguchi, L. Hamilton and J. W. Jones, Cooperative self-assembly of dendrimers via pseudorotaxane formation from a homotritopic guest molecule and complementary monotopic host dendrons, J. Am. Chem. Soc., 2002, 124, 4653–4665.
S.-H. Chiu, S. J. Rowan, S. J. Cantrill, J. F. Stoddart, A. J. P. White and D. J. Williams, Chem. Commun., 2002, 2948–2949.
O. P. Kryatova, S. V. Kryatov, R. J. Staples and E. V. Rybak-Akimova, Stable supramolecular dimer of self-complementary benzo-18-crown-6 with a pendant protonated amino arm, Chem. Commun., 2002, 3014–3015.
O. P. Kryatova, I. V. Korendovych and E. V. Rybak-Akimova, Proton-induced supramolecular dimerization of aminomethylbenzo-15-crown-5 accompanied by a covalent dimerization of cyanoborohydride anion, Tetrahedron Lett., 2003, 44, 4251–4255.
T. Akutagawa, T. Hasegawa, T. Nakamura and T. Inabe, Supramolec-ular cation assemblies of hydrogen-bonded (NH4+/NH2NH3+) (Crown ether) in [Ni(dmit)2]-based molecular conductors and magnets, J. A m. Chem. Soc., 2002, 124, 8903–8911.
T. Akutagawa, A. Hashimoto, S. Nishihara, T. Hasegawa and T. Nakamura, Magnetic properties of [Ni(dmit)2]−Anions induced by flexible hydrogen-bonded supramolecular cations [(p-Xylylenediammonium)0.5(crown ethers)]+, J. Phys. Chem. B, 2003, 107, 66–74.
H. Sharghi, M. A. Nasseri and K. Niknam, Phenol-containing macro-cyclic diamides as new catalysts in the highly regioselective conversion of epoxides toβ-hydroxythiocyanates, J. Org. Chem., 2001, 66, 7287–7293.
R. M. Izatt, J. S. Bradshaw, S. A. Nielsen, J. D. Lamb and J. J. Christensen, Thermodynamic and kinetic data for cation-macrocycle interaction, Chem. Rev., 1985, 85, 271–339.
R. M. Izatt, K. Pawlak, J. S. Bradshaw and R. L. Bruening, Thermo-dynamic and kinetic data for macrocycle interactions with cations and anions, Chem. Rev., 1991, 91, 1721–2085.
H.-J. Buschmann, L. Mutihac and K. Jansen, Complexation of some amine compounds by macrocyclic receptors, J. Inclusion Phenom. Macrocyclic Chem., 2001, 39, 1–11.
K. M. Doxsee, P. E. J. Francis and T. J. R. Weakley, Hydration, ion pairing, and sandwich motifs in ammonium nitrate of crown ethers, Tetrahedron, 2000, 56, 6683–6691.
B. F. G. Johnson, C. M. G. Judkins, J. M. Matters, D. S. Shephard and S. Parsons, New linked and threaded cluster compounds, Chem. Commun., 2000, 1549–1550.
H. Tsukube, M. Wada, S. Shinoda and H. Tamiaki, Porphyrinatoerbium-crown ether conjugate for synergistic binding and chirality sensing of zwitterionic amino acids, Chem. Commun., 1999, 1007–1008.
M. D. Barboiu, N. D. Hovnanian, C. Luka and L. Cot, Functionalized derivatives of benzocrown-ethers, V. Multiple, molecular recognition of zwitterionic phenylalanine, Tetrahedron, 1999, 55, 9221–9232.
Y. Machida, M. Kagawa and H. Nishi, Nuclear magnetic resonance studies for the chiral recognition of (+)-(R)-18-crown-6-tetracarboxylic acid to amino compounds, J. Pharm. Biomed. Anal., 2003, 30, 1929–1942.
K. Tsubaki, H. Tanaka, H. Morikawa and K. Fuji, Synthesis and recognition of amino acids by binaphthyl-crown receptors, Tetrahedron, 2003, 59, 3195–3199.
A. P. de Silva, H. Q. Gunaratne, C. McVeigh, G. E. Maguire, P. R. S. Maxwell and E. O’Hanlon, Fluorescent signalling of the brain neurotransmitter γ-aminobutyric acid and related amino acid zwitterions, Chem. Commun., 1996, 2191–2192.
F. P. Schmidtchen, Tetazac: a novel artificial receptor for binding omega-amino carboxylates, J. Org. Chem., 1986, 51, 5161–5168.
O. A. Fedorova, E. N. Andryukhina, Yu. V. Fedorov, M. A. Panfilov, M. V. Alfimov, G. Jonusauskas, A. Grelard and E. Dufourc, Supramolec-ular assemblies of crown-containing 2-styrylbenzothiazole with amino acids, Org. Biomol. Chem., 2006, 4, 1007–1013.
M. Czekalla, H. Stephan, B. Habermann, J. Trepte, K. Gloe and F. P. Schmidtchen, Complexation studies of zwitterionic amino acids with crown and guanidinium compounds using titration calorimetry, Thermochim. Acta, 1998, 313, 137–144.
A. Späth and B. König, Ditopic crown ether-guanidinium ion receptors for the molecular recognition of amino acids and small peptides, Tetrahedron, 2010, 66, 1859–1873.
M. Inouye, M. Ueno, K. Tsuchiya, N. Nakayama, T. Konishi and T. Kitao, Alkali-metal cation recognition induced isomerization of spirobenzopyrans and spirobenzonaphthoxazins possessing a crown ring as a recognition site: multifunctional artificial receptors, J. Org. Chem., 1992, 57, 5377–5383.
S. Shinkai, T. Minami, Y. Kusano and O. Manabe, Photoresponsive crown ethers. 8. Azobenzenophane-type “switched-on” crown ethers which exhibit an all-or-nothing change in ion-binding ability, J. Am. Chem. Soc., 1983, 105, 1851–1856.
M. Tanaka, K. Kamada, H. Ando, T. Kitagaki, Ya. Shibuyani and K. Kimura, Synthesis and photochromism of crowned spirobenzoth-iapyran: Facilitated photoisomerization by cooperative complexation by crown ether and thiaphenolate moieties with metal ions, J. Org. Chem., 2000, 65, 4243–4247.
M. Nakamura, T. Fujioka, H. Sakamoto and K. Kimura, High stability constants for multivalent metal ion complexes of crown ether derivatives incorporating two spirobenzopyran moieties, New J. Chem., 2002, 26, 554–559.
M. V. Alfimov, O. A. Fedorova and S. P. Gromov, Photoswitchable molecular receptors, J. Photochem. Photobiol., A, 2003, 158, 183–198.
M. Nakamura, K. Takahashia, T. Fujiokaa, S. Kadoa, H. Sakamoto and K. Kimura, Evaluation of photoinduced changes in stability constants for metal-ion complexes of crowned spirobenzopyran derivatives by electrospray ionization mass spectrometry, J. Am. Soc. Mass Spectrom., 2003, 14, 1110–1115.
K. Kimura, H. Sakamoto and M. Nakamura, Molecular design and applications of photochromic crown compounds-How can we manipulate metal ions photochemically?, Bull. Chem. Soc. Jpn., 2003, 76, 225–235.
O. A. Fedorova, E. N. Ushakov, Yu. V. Fedorov, Y. P. Strokach and S. P. Gromov, in Macrocyclic Chemistry: Current Trends and Future Perspetives, ed. K. Gloe, Springer, Dordrecht, Berlin, 2005, pp. 235–252.
A. V. Tsukanov, A. D. Dubonosov, V. A. Bren and V. I. Minkin, Organic chemosensors with crown-ether groups (review), Chem. Heterocycl. Compd., 2008, 44, 899–923.
A. I. Vedernikov, S. P. Gromov, N. A. Lobova, L. G. Kuzmina, Yu. A. Strelenko, J. A. #xX_CYR_HEX_41a;. Howard and M. V. Alfimov, Photosensitive molecular tweezers. Synthesis and homoditopic complex formation of a bisstyryl dye containing two crown ether fragments with diammonium salts, Russ. Chem. Bull., 2005, 54, 666.
W. H. Melhuish, A standard fluorescence spectrum for calibrating spectrofluorometers, J. Phys. Chem., 1961, 65, 229–235.
S. R. Meech and D. Phillips, Photophysics of some common fluorescence standards, J. Photochem., 1983, 23, 193–217.
P. Gans, A. Sabatini and A. Vacca, Investigation of equilibria in solution. Determination of equilibrium constants with the HYPER-QUARD suite of programs, Talanta, 1996, 43, 1739–1753.
See, for example: (a) M. V. Gromov, S. P. Fedorov, Y. V. Fedorova, O. A. Vedernikov, A. I. Churakov, V. Kuz’mina, L G. Howard, J. A. K. Bossmann, S. Braun, M. A. Woerner, D. F. Sears Jr. and J. Saltiel, Synthesis, Structure and Ion Selective Complexation of Trans and Cis Isomers of Photochromic Dithia-18-crown-6 Ethers, J. Am. Chem. Soc., 1999, 121, 4992–5000
Yu. Fedorov, O. Fedorova, N. Schepel, S. Gromov, M. V. Alfimov, A. M. Turek and J. Saltiel, Synthesis and multitopic complex formation of a photochromic bis-crown ether based on benzobis(thiazole), J. Phys. Chem, 2005, 109, 8653–8660.
G. Favaro, U. Mazzucato and F. Masetti, Excited State Reactivity of Aza Aromatics. I. Basicity, of 3-Styrylpyridines in the First Excited Singlet State, J. Phys. Chem., 1973, 77, 601–604
G. Bartocci, P. Bortolus and U. Mazzucato, Excited State Reactivity of Aza Aromatics. II. Solvent, and Protonation Effects on Photoisomerization and Luminescence of Styrylpyridines, J. Phys. Chem., 1973, 77, 605–610.
A. Kütt, I. Leito, I. Kaljurand, L. Sooväli, V. M. Vlasov, L. M. Yagupolskii and I. A. Koppel, A Comprehensive Self-Consistent Spec-trophotometric Acidity Scale of Neutral Brønsted Acids in Acetonitrile, J. Org. Chem., 2006, 71, 2829–2838.
S. Boyd, J. R. Brannan, H. S. Dunsmore and G. H. J. Nancollas, J. Chem. Eng. Data, 1967, 12, 601.
I. Sovago, T. Kiss and A. Gergely, Critical survey of the stability constants of complexes of aliphatic amino acids, Pure Appl. Chem., 1993, 65, 1029–1080.
W. Carr and W. J. Shutt, Dielectric properties and ionization constants of amino acids, Trans. Faraday Soc., 1939, 35, 579–587.
Ionization constants and stability constants of copper(II) complexes of some amino acids and their sulfur-containing analogs:; (b) Hoppe-Seyler’s, Hoppe-Seyler’s Z. Physiol. Chem., 1968, 349, 390–4.
I. Kaljurand, A. Kütt, L. Sooväli, T. Rodima, V. Mäemets, I. Leito and I. A. Koppel, Extension of the Self-Consistent Spectrophotometric Basicity Scale in Acetonitrile to a Full Span of 28 pKa Units: Unification of Different Basicity Scales, J. Org. Chem., 2005, 70, 1019–1028.
J. F. Coetzee and D. K. McGuire, Relative Basicities of Nitriles, Acetone, and Water as Solvents, J. Phys. Chem., 1963, 67, 1810–1814.
T. Fujinaga and I. Sakamoto, Electrochemical studies of sulfonates in non-aqueous solvents. Part III. Trifluoromethanesulfonic, acid as a strong acid in dipolar aprotic solvents and acetic acid, J. Electroanal. Chem., 1977, 85, 185–201.
J. Zhang, Y. Sun, C. Mao, H. Gao, W. Zhou and Z. Zhou, Theoretical study of the pKa for perchloric acid, THEOCHEM, 2009, 906, 46–49.
U. Mazzucato and A. Spalletti, Protonation effect on the excited state behaviour of E,E-1-(n-pyridyl)-4-phenylbutadienes (n = 2, 3 and 4), Photochem. Photobiol. Sci., 2003, 2, 282–288.
J. D. Baldeschwieller and E. W. Randall, Measurement of Chemical Shifts by Nuclear Magnetic Double Resonance, Proc. Chem. Soc., 1961, 303.
K. Tsubaki, H. Tanaka, T. Furuta, T. Kinoshita and K. Fuji, Recognition of the chain length ofa,w-diamines by a meso-ternaphthalene derivative with two crown ethers, Tetrahedron Lett., 2000, 41, 6089–6093.
V. M. S. Gill and J. N. Murrell, Interpretation of the Proton and Nitrogen Chemical Shifts of Pyridine and Pyridinium Cation, Trans. Faraday Soc., 1964, 60, 248–255.
M. W. Mosher, C. B. Sharma and M. R. Chakrabarty, Proton Magnetic Resonance of Some Methyl-Substituted Pyridines and Pyri-dinium Ions in Aqueous Solutions, J. Magn. Res., 1972, 7, 247–252.
E. Fischer, Calculation of Photostationary States in Systems ADB When Only A Is Known, J. Phys. Chem., 1967, 71, 3704.
D. G. Whitten and M. T. McCall, Radiationless Processes in the Photochemistry of Stilbazoles and 1,2-Bispyridylethylenes, J. Am. Chem. Soc., 1969, 91, 5097–5103.
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Electronic supplementary information (ESI) available: UV spectral sets for E-1 titrations and 1H NMR data. See DOI: 10.1039/c1pp05007a
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Fedorova, O.A., Fedorov, Y.V., Labazava, I.E. et al. Complexes of amino acids with a crown-ether derivative of 4-styrylpyridine. Monotopic or ditopic?. Photochem Photobiol Sci 10, 1954–1962 (2011). https://doi.org/10.1039/c1pp05007a
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DOI: https://doi.org/10.1039/c1pp05007a