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

3. Supermolecules substratereceptor guest host

4. CALIX[4]ARENES

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

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

10. 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. 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. ELECTROPNEUMATIC VALVE SPLITTER FUSED SILICA COLUMN VIAL WITH SAMPLE THERMOSTATE DEVICE OF STATIC HEADSPACE GAS CHROMATOGRAPHIC ANALYSIS solid phase binding of vapors in comparable conditions

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

12. p-tert-Butylcalix[4]arene 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 Brouwer, E. B.; Udachin, K. A.; Enright, G. D.; Ripmeester J. A. et al Chem. Commun. 2001, 565 Brouwer, E. B et al Phys. Chem. Chem. Phys. 1999, 1, 4043

13. c-C 8 H 16 46 c-C 7 H 14 45 c-C 6 H 12 44 c-C 5 H 10 43 c-C 4 H 8 42 1,2,4-C 6 H 3 Cl 3 41 AmCOOMe40 2-Heptanone39 C 6 H 5 Br38 c-C 6 H 11 Cl37 c-C 6 H 11 NH 2 36 BuCOOMe35 MeCOOBu34 C 6 H 5 Cl33 C 6 H 5 CH 3 32 n-BuCOMe31 c-C 6 H 11 OH30 1-BuBr29 n-BuCOMe28 C 6 H 5 OH27 MeCOOPr26 CCl 4 25 C6H6C6H6 24 1-BuCl23 Cl 2 C=CHCl22 Furfural21 PrCOMe20 C5H5NC5H5N19 EtI18 1-PrSH17 (MeCO) 2 O16 Et 2 O15 MeCOOEt14 EtCOOMe13 1-BuOH12 CS 2 11 EtCOMe10 CHCl 3 9 THF8 MeI7 EtBr6 1-PrOH5 MeCOOMe4 Me 2 CO3 EtOH2 MeOH1  Gsolv, kJ/mol = -0.702 MR D + 14.0 R=0.9910, n=46,  =1.1 B.N.Solomonov, V.V.Gorbatchuk, A.I. Konovalov. Zh. Obsch. Khim. 1981, Vol. 51, P.2688-2693.

14. -  H solv / kJ/mol = 5.09 + 1.03 MR D n=102, r=0.994,  =1.56

15. 1CH 3 OH 14c-Hexane20C 6 H 5 OCH 3 2CH 3 CN 15n-Hexane21n-Heptane 3EtOH 16Pinacolone22o-Xylene 5EtCN 17Toluene23C 6 H 5 Et 6(CH 3 ) 2 CO 18t-BuOAc24n-Octane 7n-PrOH 8CHCl 3 91,4-Dioxane 10n-Pentane 11n-BuCl 12C6H6C6H6 13CCl 4 19C 6 H 5 NO 2 25n-Nonane 2 : 1 guest / host 1 : 1 1 : 2 S~1~ const V. V. Gorbatchuk, A. G. Tsifarkin, I. S. Antipin, B. N. Solomonov and A. I. Konovalov, Mendeleev Commun., 1999, 11 Stoichiometry - guest size 1 MeOH5 Me 2 CO 2 MeCN6 CH 2 Cl 2 3 MeNO 2 7 CHCl 3 4 EtCN8 CCl 4 Lit.data (X-ray) 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. p-tert-Butylcalix[4]arene 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 Brouwer, E. B.; Udachin, K. A.; Enright, G. D.; Ripmeester J. A.; Ooms, K. J.; Halchuk P. A. Chem. Commun. 2001, 565 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

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

18. 1CH 3 OH 14c-Hexane20C 6 H 5 OCH 3 2CH 3 CN 15n-Hexane21n-Heptane 3EtOH 16Pinacolone22o-Xylene 5EtCN 17Toluene23C 6 H 5 Et 6(CH 3 ) 2 CO 18t-BuOAc24n-Octane 7n-PrOH 8CHCl 3 91,4-Dioxane 10n-Pentane 11n-BuCl 12C6H6C6H6 13CCl 4 19C 6 H 5 NO 2 25n-Nonane 2 : 1 guest / host 1 : 1 1 : 2 S~1~ const V. V. Gorbatchuk, A. G. Tsifarkin, I. S. Antipin, B. N. Solomonov and A. I. Konovalov, Mendeleev Commun., 1999, 11 Stoichiometry - guest size 1 MeOH5 Me 2 CO 2 MeCN6 CH 2 Cl 2 3 MeNO 2 7 CHCl 3 4 EtCN8 CCl 4 Lit.data (X-ray) 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. 1 MeOH 7 CHCl 3 2 MeCN 8 1,4-Dioxane 3 EtCN 9 Pyridine 4 Me 2 CO 10 C 6 H 6 5 1-PrOH 11 CCl 4 6 1-PrCN 12 Et 3 N Stoichiometry - guest size 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 T=298 K O O O O H H H H S – inclusion stoichiometry N – cooperativity constant Hill equation inclusion threshold: = RT(lnC)/N - inclusion free energy

22. N Guest MR D  G c (vap) 1 MeOH 8.3-5.7-4.8-6.5 2 CH 3 CN 11.1-9.3-7.3-7.9 3 EtOH 12.9-8.6*-6.9 4 EtCN 16-12.1-8.1-9.5 5 Me 2 CO 16.1-4.8-4.2-4.9 6 CH 2 Cl 2 16.3-10.3-3.5- 7 1-PrOH 17.5-11.4*-9.7 8 n-PrCN 20.4-11.9*-11.1 9 CHCl 3 21.3-5.6-4.5-5.1 10 C5H5NC5H5N 24.1-17.0*-13.3 11 C6H6C6H6 26.2-12.4*-6.5 12 CCl 4 26.4-8.6-5.1-5.8 13 c-C 6 H 12 27.7-10.5** 14 n-C6H14 29.9-8.7** 15 Pinacolone 30-9.9** 16 PhCH 3 31.1-13.7** 17 t-BuOAc 31.7-10.6** 18 PhOCH 3 32.9-19.8** 19 Et 3 N 33.8-12.4*-8.5 20 n-C 7 H 16 34.5-11.8** 21 o-C 6 H 4 Me 2 35.9-14.5** 22 n-C 8 H 18 39.2-14.2** 23 n-C 9 H 20 43.8-15.3** 24 MeNO 2 12.9*-9.3- 25 Dioxane 21.7-*-10.0 * no binding - not determined

23. Guest vapor solid host-guest compound  G c (vap) O O O O H H H H

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

25. Guest vapor toluene solution  G solv Alcohols, ketones, esters, anisole Nitriles, pyridine, triethylamine polychloromethanes Benzene, toluene, o-xylene n-alcanes, cyclohexane

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

27. Guest vapor solution  G solv = +  G cav  G int Solvation process cavity formationinteraction

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

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

30.  G trans toluene solution solid host-guest compound MeOH, acetone MeCN, EtCN polychloromethanes nitromethane  G trans /kJ mol -1 = -12.24 + 0.568MR D (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

32. Alcohols, acetone, dioxane MeCN, EtCN, PrCN, pyridine, Et 3 N CHCl 3, CCl 4 benzene  G trans /kJ mol -1 = -5.58 + 0.200MR D + 0.391  G H MeOH (n = 13, r = 0.955, RSD = 0.8)  G trans /kJ mol -1 = -5.76 + 0.204MR D + 0.236  G H PhOH (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

33. 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. LhotakVSHT Prague, Czech Rep. Support from RFBR (grants № 00-15-97411, 01-03-32079)