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Chemistry

THERMODYNAMICS OF MOLECULAR RECOGNITION AND DESIGN OF SUPRAMOLECULAR ARCHITECTURES ON THE BASIS OF CALIXARENES A.I.Konovalov , V.V.Gorbatchuk, I.S.Antipin A.E.Arbuzov Institute of Organic and Physical Chemistry, Kazan Kazan State University. Radicals Ions Ion-radicals. A―B C―D.

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Chemistry

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  1. THERMODYNAMICS OF MOLECULAR RECOGNITION AND DESIGN OF SUPRAMOLECULAR ARCHITECTURES ON THE BASIS OF CALIXARENES A.I.Konovalov, V.V.Gorbatchuk, I.S.Antipin A.E.Arbuzov Institute of Organic and Physical Chemistry, Kazan Kazan State University

  2. Radicals Ions Ion-radicals A―B C―D AB + CD → Chemistry supramolecular molecular Specific and nonspecific interactions: intermolecular binding Covalent interactions: intramolecular binding molecules →supermolecules atoms →molecules Supramolecular assemblies A + B → A―B

  3. Supermolecules substrate receptor guest host

  4. CALIX[4]ARENES

  5. H+ 1872 – A.Bayer + H-CHO polymer products 1944 – A.Zinke, E.Zigler H+ + R-CHO OH- 1978 – C.D.Gutsche + H-CHO n=4-8 1997 – H.Kumagai et al NaOH D + S8

  6. R R R R HO OH OH HO R R R R HO OH OH HO

  7. Brouwer, E. B.et al. Phys. Chem. Chem. Phys.1999, 1, 4043 Brouwer, E. B.; Enright, G. D.; Ratcliffe, C. I.; Facey, G. A.; Ripmeester, J. A. J. Phys. Chem.1999, 103, 10604

  8. Calixarenes in Action (Eds. L. Mandolini, R. Ungaro), Imperial College Press. – 2000. -250 p.

  9. Vapor phase HOST GUEST Solid phase Problem: ‘Structure – thermodynamic property’ relationship for inclusion of volatile organic compounds by solid hosts Experimental method Static method of GC headspace analysis Experimental data vapor sorption isotherms Results Inclusion stoichiometry, free energy, cooperativity Variation of host and guest molecular structure

  10. ELECTROPNEUMATICVALVE SPLITTER FUSED SILICA COLUMN VIAL WITH SAMPLE THERMOSTATE DEVICE OF STATIC HEADSPACE GAS CHROMATOGRAPHIC ANALYSIS Electropneumatic dosing B. Kolb, P. Pospisil, T. Borath and M. Auer, J. High Res. Chromatogr. & Chromatogr. Commun., 1979, 2, 283. Activity determination A. Hussam and P. W. Carr, Anal. Chem., 1985, 57, 793. Data examples J. H. Park, A. Hussam, P. Couasnon, D. Fritz and P. W. Carr, Anal. Chem., 1987, 59, 1970. solid phase binding of vapors in comparable conditions

  11. Isotherms O O H H O O O O O H O H H H H H Hill equation S – inclusion stoichiometry N – cooperativity constant inclusion threshold: T=298 K = RT(lnC)/N - inclusion free energy

  12. Brouwer, E. B.; Udachin, K. A.; Enright, G. D.; Ripmeester J. A.et alChem. Commun.2001, 565 p-tert-Butylcalix[4]arene Brouwer, E. Bet alPhys. Chem. Chem. Phys.1999, 1, 4043 1:1 host-guest complex of p-tert-butylcalix[4]arene with fluorobenzene 2:1 host-guest complex of p-tert-butylcalix[4]arene with 1-octanol

  13. 17 1-PrSH 18 EtI 19 C5H5N 20 PrCOMe 21 Furfural 22 Cl2C=CHCl 23 1-BuCl 24 C6H6 25 CCl4 26 MeCOOPr 27 C6H5OH 28 n-BuCOMe 29 1-BuBr 30 c-C6H11OH 1 MeOH 31 n-BuCOMe 2 EtOH 32 C6H5CH3 3 Me2CO 33 C6H5Cl 4 MeCOOMe 34 MeCOOBu 5 1-PrOH 35 BuCOOMe 6 EtBr 36 c-C6H11NH2 7 MeI 37 c-C6H11Cl 8 THF 38 C6H5Br 9 CHCl3 39 2-Heptanone 10 EtCOMe 40 AmCOOMe 11 CS2 41 1,2,4-C6H3Cl3 12 1-BuOH 42 c-C4H8 13 EtCOOMe 43 c-C5H10 14 MeCOOEt 44 c-C6H12 15 Et2O 45 c-C7H14 16 (MeCO)2O 46 c-C8H16 B.N.Solomonov, V.V.Gorbatchuk, A.I. Konovalov. Zh. Obsch. Khim. 1981, Vol. 51, P.2688-2693. DGsolv, kJ/mol = -0.702 MRD + 14.0 R=0.9910, n=46, d=1.1

  14. -DHsolv / kJ/mol = 5.09 + 1.03 MRD n=102, r=0.994, d=1.56

  15. Stoichiometry - guest size 2 : 1 guest / host 1 CH3OH 8 CHCl3 2 CH3CN 9 1,4-Dioxane 3 EtOH 10 n-Pentane 5 EtCN 11 n-BuCl 1 : 1 6 (CH3)2CO 12 C6H6 7 n-PrOH 13 CCl4 14 c-Hexane 20 C6H5OCH3 1 : 2 15 n-Hexane 21 n-Heptane 16 Pinacolone 22 o-Xylene 17 Toluene 23 C6H5Et 18 t-BuOAc 24 n-Octane 19 C6H5NO2 25 n-Nonane V. V. Gorbatchuk, A. G. Tsifarkin, I. S. Antipin, B. N. Solomonov and A. I. Konovalov, Mendeleev Commun., 1999, 11 • Lit.data (X-ray) 1 MeOH 5 Me2CO 2 MeCN 6 CH2Cl2 3 MeNO2 7 CHCl3 4 EtCN 8 CCl4 S~1~ const V. V. Gorbatchuk, A. G. Tsifarkin, I. S. Antipin, B. N. Solomonov, A. I. Konovalov, P.Lhotak, I.Stibor J. Phys. Chem.B. , 2002, 106(23); 5845-5851

  16. Brouwer, E. B.; Udachin, K. A.; Enright, G. D.; Ripmeester J. A.; Ooms, K. J.; Halchuk P. A. Chem. Commun.2001, 565 p-tert-Butylcalix[4]arene Brouwer, E. B.; Gougeon, R. D. M.; Hirschinger, J.; Udachin, K. A.; Harris, R. K.; Enright, G. D.; Ripmeester, J. A. Phys. Chem. Chem. Phys.1999, 1, 4043 1:1 host-guest complex of p-tert-butylcalix[4]arene with fluorobenzene 2:1 host-guest complex of p-tert-butylcalix[4]arene with 1-octanol

  17. All-transn-hexane, 1-chlorobutane, 1,4-dichlorobutane and 1,4 dichlorobenzene All-transn-hexane, 1-heptanol, 1-octanol and dodecane K. A. Udachin et al. /J. Supramol. Chem. 1 (2001) 97–100

  18. Stoichiometry - guest size 2 : 1 guest / host 1 CH3OH 8 CHCl3 2 CH3CN 9 1,4-Dioxane 3 EtOH 10 n-Pentane 5 EtCN 11 n-BuCl 1 : 1 6 (CH3)2CO 12 C6H6 7 n-PrOH 13 CCl4 14 c-Hexane 20 C6H5OCH3 1 : 2 15 n-Hexane 21 n-Heptane 16 Pinacolone 22 o-Xylene 17 Toluene 23 C6H5Et 18 t-BuOAc 24 n-Octane 19 C6H5NO2 25 n-Nonane V. V. Gorbatchuk, A. G. Tsifarkin, I. S. Antipin, B. N. Solomonov and A. I. Konovalov, Mendeleev Commun., 1999, 11 • Lit.data (X-ray) 1 MeOH 5 Me2CO 2 MeCN 6 CH2Cl2 3 MeNO2 7 CHCl3 4 EtCN 8 CCl4 S~1~ const V. V. Gorbatchuk, A. G. Tsifarkin, I. S. Antipin, B. N. Solomonov, A. I. Konovalov, P.Lhotak, I.Stibor J. Phys. Chem.B. , 2002, 106(23); 5845-5851

  19. Akdas, H.; Bringel, L.; Graf, E.; Hosseini, M. W.; Mislin, G.; Pansanel, J.; de Cian, A.; Fischer, J. Tetrahedron Lett.1998, 39, 2311

  20. Stoichiometry - guest size 1 MeOH 7 CHCl3 2 MeCN 8 1,4-Dioxane 3 EtCN 9 Pyridine 4 Me2CO 10 C6H6 5 1-PrOH 11 CCl4 6 1-PrCN 12 Et3N V. V. Gorbatchuk, A. G. Tsifarkin, I. S. Antipin, B. N. Solomonov, A. I. Konovalov, J. Seidel, F. Baitalov, J. Chem.Soc.Perkin Trans. 2, 2000, N11, P.2287-2294 L. J. Barbour, S. A. Bourne, M. R. Caira, L. R. Nassimbeni, E. Weber, K. Skobridis and A. Wierig, Supramol. Chem., 1993, 1, 331

  21. Isotherms O O H H O O O O O H O H H H H H Hill equation S – inclusion stoichiometry N – cooperativity constant inclusion threshold: T=298 K = RT(lnC)/N - inclusion free energy

  22. * no binding - not determined

  23. O H O O H O H H Guest vapor DGc(vap) solid host-guest compound

  24. O H O O H O H H Guest vapor DGc(vap) solid host-guest compound Alcohols, ketones, esters, anisole Benzene, toluene, o-xylene Nitriles, pyridine, triethylamine n-alcanes, cyclohexane polychloromethanes

  25. Guest vapor DGsolv toluenesolution Alcohols, ketones, esters, anisole Benzene, toluene, o-xylene Nitriles, pyridine, triethylamine n-alcanes, cyclohexane polychloromethanes

  26. Alcohols, ketones, esters, anisole Nitriles, pyridine, triethylamine polychloromethanes Benzene, toluene, o-xylene n-alcanes, cyclohexane

  27. Solvation process Guest vapor DGsolv DGcav + DGint = solution cavity formation interaction

  28. O H O O H O H H toluene solution DGtrans Alcohols, ketones, esters, anisole Benzene, toluene, o-xylene solid host-guest compound Nitriles, pyridine, triethylamine n-alcanes, cyclohexane polychloromethanes

  29. Guest vapor DGc(vap) solid host-guest compound polychloromethanes MeOH, acetone nitromethane MeCN, EtCN

  30. toluene solution DGtrans MeOH, acetone polychloromethanes solid host-guest compound MeCN, EtCN nitromethane Gtrans/kJ mol-1 = -12.24 + 0.568MRD (n = 7, r = 0.972, RSD = 0.6) V. V. Gorbatchuk, A. G. Tsifarkin, I. S. Antipin, B. N. Solomonov, A. I. Konovalov, P.Lhotak, I.Stibor J. Phys. Chem.B. , 2002, 106(23); 5845-5851

  31. Alcohols, acetone, dioxane CHCl3, CCl4 MeCN, EtCN, PrCN, pyridine, Et3N benzene Gtrans/kJ mol-1 = -5.58 + 0.200MRD + 0.391GHMeOH (n = 13, r = 0.955, RSD = 0.8) Gtrans /kJ mol-1 = -5.76 + 0.204MRD + 0.236GHPhOH (n = 13, r = 0.954, RSD = 0.8) V. V. Gorbatchuk, A. G. Tsifarkin, I. S. Antipin, B. N. Solomonov, A. I. Konovalov, J. Seidel, F. Baitalov, J. Chem.Soc.Perkin Trans. 2, 2000, N11, P.2287-2294

  32. Dr.Gorbatchuk V.V. Prof.Antipin I.S. Dr.Tsifarkin A.G. Dr.Ziganshin M.A. Prof.Solomonov B.N. Group cooperates with W.Habicher TU Dresden, Germany J.Seidel TU BA Freiberg, Germany I.Stibor, P. Lhotak VSHT Prague, Czech Rep. Support from RFBR (grants № 00-15-97411, 01-03-32079)

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