Abstract
Eight water insoluble complexes of tetramethylsulfonated calix[4]resorcinarenes 1 and 2 (–CH3 and –C5H11) with phenothiazine derivative, 3, were obtained under substoichiometric conditions by mixing aqueous solutions of the initial reagents. It was found that complexation of cationic 3 by macrocycles was provided by both Coulomb interaction with the negative sulfonato-groups on the upper rim and by cation-π interactions with the aromatic cavity. The complexes precipitated and, therefore, were studied in organic solvents—DMSO, CD3OD, and CDCl3 using IR-, UV-, and NMR- spectroscopy. Formation of the complexes accompanied by gradual dehydratation of the host—estimated quantity of water in the complexes decreased with increase of the initial concentration of 3. Driving forces of precipitation and complexation, the role of water coordinated by the hosts, and distribution of phenothiazine derivative between two kinds of binding sites are discussed.
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Acknowledgments
We thank Collaboration linkage grant of NATO (PCT.CLG.979178) and Russian Foundation of Basic Research for financial support of this work (RFBR 06-03-32189a and 05-03-32558-a)). We are also grateful to Prof. Wolf D. Habicher and Mrs. Margaret Grüner from TU Dresden for active support of the experimental part of the present research.
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Appendix
Appendix
1H NMR spectrum (600 MHz, 30 °C) of 6, 10 mM in DMSO-d6
Table A1 Chemical shifts δ(ppm) of protons of free and complexed 3
Table A2 Chemical shifts δ(ppm) of protons of macrocycles 1 and 2 and their complexes
Table A3 13C NMR-spectra of 1 and 3 and their complexes 4–7 in DMSO-d6, δ, ppm
Table A4 13C NMR-spectra of 2, 3, and complexes 8–10 in DMSO-d6 δ, ppm
Table A5 Solubilitya and melting point (°C) of initial compounds 1 and 3 and their complexes (1&3)
Table A6 IR-spectra of 1, 2 and 3 and their complexes 1&3 (4–7) and 2&3 (8–10) (KBr)
Table A7 UV-spectra of 1, 2, 3 and their complexes 1&3 (4–7) and 2&3 (8–10) (0.1 mmol l−1, MeOH) (λ, nm; log ε)
Table A8 Stoichiometry of ionic complexes of the macrocycle 2 (2&3) determined from 1H NMR spectra in DMSO (30 °C)
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Kazakova, E.K., Syakaev, V.V., Morozova, J.E. et al. Stable complexes of tertiary ammonia derivative of phenothiazine with tertramethylsulfonated resorcin[4]arenes obtained under substoichiometric conditions. J Incl Phenom Macrocycl Chem 59, 143–154 (2007). https://doi.org/10.1007/s10847-007-9307-2
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DOI: https://doi.org/10.1007/s10847-007-9307-2