1. THE ROLE OF CRYSTALLINE ENVIRONMENT IN THE INTRAMOLECULAR REACTIONS Elena V. Boldyreva REC-008 MDEST Novosibirsk State University & Institute of Solid State Chemistry RAS boldyrev@nsu.ru

2.  Introduction  Effects of the environment  Response of the environment  Conclusions

4. Supramolecular systems Supermolecules Supramolecular assemblies Associates (dimers) Very large molecules (proteins, DNA, RNA) solutionscrystals Supermolecules (Multisubunit proteins, nucleoproteids) Associates of supermolecules Supramolecular assemblies of supermolecules (protein crystals)

5. Supramolecular systems Supermolecules Supramolecular assemblies Associates (dimers) Very large molecules (proteins, DNA, RNA) solutionscrystals Supermolecules (Multisubunit proteins, nucleoproteids) Associates of supermolecules Supramolecular assemblies of supermolecules (protein crystals)

6. Molecular / ionic-molecular crystals Van der Waals interactions Hydrogen bonds Other specific interactions

7. on the structures of assemblies on the properties of assemblies  supramolecular synthesis  crystal engineering  statistical analyses of databases  prediction of crystal structures physical properties chemical reactivity  important for practice  intermolecular potentials response to external actions The effect of intermolecular interactions  molecular  crystal  kinetics  reaction selectivity  effects of  reaction type structures of product temperature wavelength pressure (homogeneous/heterogeneous, single-crystal  single-crystal)  cooperative effects

8. on the structures of assemblies on the properties of assemblies  supramolecular synthesis  crystal engineering  statistical analyses of databases  prediction of crystal structures physical properties chemical reactivity  important for practice  intermolecular potentials response to external actions The effect of intermolecular interactions  molecular  crystal  kinetics  reaction selectivity  effects of  reaction type structures of product temperature wavelength pressure (homogeneous/heterogeneous, single-crystal  single-crystal)  cooperative effects

9. on the structures of assemblies on the properties of assemblies  supramolecular synthesis  crystal engineering  statistical analyses of databases  prediction of crystal structures physical properties chemical reactivity  important for practice  intermolecular potentials response to external actions The effect of intermolecular interactions  molecular  crystal  kinetics  reaction selectivity  effects of  reaction type structures of product temperature wavelength pressure (homogeneous/heterogeneous, single-crystal  single-crystal)  cooperative effects

10. on the structures of assemblies on the properties of assemblies  supramolecular synthesis  crystal engineering  statistical analyses of databases  prediction of crystal structures physical properties chemical reactivity  important for practice  intermolecular potentials response to external actions The effect of intermolecular interactions  molecular  crystal  kinetics  reaction selectivity  effects of  reaction type structures of product temperature wavelength pressure (homogeneous/heterogeneous, single-crystal  single-crystal)  cooperative effects

11. on the structures of assemblies on the properties of assemblies  supramolecular synthesis  crystal engineering  statistical analyses of databases  prediction of crystal structures physical properties chemical reactivity  important for practice  intermolecular potentials response to external actions The effect of intermolecular interactions  molecular  crystal  kinetics  reaction selectivity  effects of  reaction type structures of product temperature wavelength pressure (homogeneous/heterogeneous, single-crystal  single-crystal)  cooperative effects

12. Effects of environment Steric restrictions Interactions in the second coordination sphere Cooperative phenomena Passive reaction cavity Active reaction cavity Flexible reaction cavity Feed-back phenomena

13. Two groups of problems: Effect of the environment on the reaction rate and the very possibility of the reaction Response of the environment to the reaction

14.  Introduction  Effects of the environment  Response of the environment  Conclusions

15. Variation of the environment Various outersphere anions Different polymorphs Continuous distortion of the structure (variable pressure / elastic deformation)

16. [Co(NH 3 ) 5 NO 2 ]Cl 2 [Co(NH 3 ) 5 NO 2 ]Cl(NO 3 )

17. a (a’)c0 [Co(NH 3 ) 5 NO 2 ]I 2, Pnma [Co(NH 3 ) 5 NO 2 ]I 2, C2/m

18. Effects of the environment: Changes in the mechanism Different reaction products (or no reaction at all in particular environments) Kinetics Spatial propagation (homogeneous / heterogeneous) Single crystal  single crystal / Fragmentation of crystals

19. Effects of the environment: Changes in the mechanism Different reaction products (or no reaction at all in particular environments) Kinetics Spatial propagation (homogeneous / heterogeneous) Single crystal  single crystal / Fragmentation of crystals

20. Linkage isomerization in [Co(NH 3 ) 5 NCS]Cl 2 Solution: intramolecular; crystal: intermolecular

21. Effects of the environment: Changes in the mechanism Different reaction products (or no reaction at all in particular environments) Kinetics Spatial propagation (homogeneous / heterogeneous) Single crystal  single crystal / Fragmentation of crystals

22. [Co(NH 3 ) 5 ONO]An[Co(NH 3 ) 5 NO 2 ]An An = 2Cl -, 2Br -, 2I -, 2F -, Cl - (NO 3 ) -, 2(NO 3 ) -, (SO 4 ) 2-, etc.  100% linkage isomerization h T Linkage isomerization in [Co(NH 3 ) 5 NO 2 ]An (intramolecular) Solution: Crystals: An = (C 2 O 4 ) 2-  no photoisomerization, 100% red-ox decomposition An = (SiF 6 ) 2-  photoisomerization not complete (40%), no red-ox decomposition 75% red-ox decomposition + 25% linkage isomerization

23. Effects of the environment: Changes in the mechanism Different reaction products (or no reaction at all in particular environments) Kinetics Spatial propagation (homogeneous / heterogeneous) Single crystal  single crystal / Fragmentation of crystals

24. Different outersphere species

25. Racemization of (+)-[Co(en) 3 ]X 3 050100150200t, h 0.0 0.2 0.4 0.6  Cl - SCN - Br - I-I-

26. Linkage isomerization in [Co(NH 3 ) 5 ONO]An

27. «Free space» around the nitro-ligand in [Co(NH 3 ) 5 NO 2 ]XY XY = 2Cl - XY = 2Br - XY = Cl - (NO 3 ) - XY = 2I - XY = (SiF 6 ) 2- XY = (C 2 O 4 ) 2-

28. Different polymorphs

29. [Co(NH 3 ) 5 ONO]Cl 2 [Co(NH 3 ) 5 ONO]Br 2 [Co(NH 3 ) 5 ONO]I 2 Isomerization in the different polymorphs 1 2 1 2 1 3 2

30. Continuous distortion of the same structure (hydrostatic pressure)

31. Effect of hydrostatic pressure on the linkage isomerization [Co(NH 3 ) 5 ONO]Br 2 [Co(NH 3 ) 5 NO 2 ]Br 2  k1k1 k2k2  V > 0 (!) but V # < 0 Pressure accelerates the reaction (!)

32. Effect of hydrostatic pressure on the linkage isomerization [Co(NH 3 ) 5 ONO]Br 2 [Co(NH 3 ) 5 NO 2 ]Br 2  k1k1 k2k2  V > 0 (!) but V # < 0 Pressure accelerates the reaction (!)

33. Effects of the environment: Changes in the mechanism Different reaction products (or no reaction at all in particular environments) Kinetics Spatial propagation (homogeneous / heterogeneous) Single crystal  single crystal / Fragmentation of crystals

35. Effects of the environment: Changes in the mechanism Different reaction products (or no reaction at all in particular environments) Kinetics Spatial propagation (homogeneous / heterogeneous) Single crystal  single crystal / Fragmentation of crystals

36. Linkage isomerization in [Co(NH 3 ) 5 NO 2 ]Cl(NO 3 )

37. Continuous distortion of the same structure (elastic bending) Variation of the environment

38. holder crystal mirror load laser scale light

40. Effect of elastic bending on the linkage isomerization [Co(NH 3 ) 5 NO 2 ]Cl(NO 3 ) [Co(NH 3 ) 5 ONO]Cl(NO 3 )   V < 0 (!) but V # > 0 Quantum yield decreases (!) in the elastically compressed parts of the crystals h

41. Effect of elastic bending on the linkage isomerization [Co(NH 3 ) 5 NO 2 ]Cl(NO 3 ) [Co(NH 3 ) 5 ONO]Cl(NO 3 )   V < 0 (!) but V # > 0 Quantum yield decreases (!) in the elastically compressed parts of the crystals h

42.  Introduction  Effects of the environment  Response of the environment  Conclusions

43. Effects of the environment: Changes in the mechanism Different reaction products (or no reaction at all in particular environments) Kinetics Spatial propagation (homogeneous / heterogeneous) Single crystal -> single crystal / Fragmentation of crystals

44. Response of the environment:  Changes in the mechanism  Different reaction products (or no reaction at all in particular environments)  Kinetics  Spatial propagation (homogeneous / heterogeneous)  Single crystal  single crystal / Fragmentation of crystals

45. Response: Macroscopic level Bending Fragmentation Microscopic level Changes in the interatomic distances  Shifts in the vibrational spectra  Lattice strain

46. Response: Macroscopic level Bending Fragmentation Microscopic level Changes in the interatomic distances  Shifts in the vibrational spectra  Lattice strain

47. Linear strain induced by [Co(NH 3 ) 5 NO 2 ]XY  [Co(NH 3 ) 5 ONO]XY linkage isomerization

48. Hydrostatic pressure Nitro - nitrito linkage photoisomerization

49. Linear strain in directions of atom-atom contacts in the structure of [Co(NH 3 ) 5 NO 2 ]Cl(NO 3 ) Nitro - nitrito linkage photoisomerization Hydrostatic pressure

50. Effect of elastic bending on the linkage isomerization [Co(NH 3 ) 5 NO 2 ]Cl(NO 3 ) [Co(NH 3 ) 5 ONO]Cl(NO 3 )   V < 0 (!) but V # > 0 Quantum yield decreases (!) in the elastically compressed parts of the crystals h

51. [Co(NH 3 ) 5 ONO]Br 2 Nitrito-nitro linkage thermal isomerization Hydrostatic pressure

52. Effect of hydrostatic pressure on the linkage isomerization [Co(NH 3 ) 5 ONO]Br 2 [Co(NH 3 ) 5 NO 2 ]Br 2  k1k1 k2k2  V > 0 (!) but V # < 0 Pressure accelerates the reaction (!)

53.  Introduction  Effects of the environment  Response of the environment  Conclusions

54. “Реакция неотделима от среды, в которой она протекает” Н. Меншуткин, 1890 г.

55. “A reaction cannot be separated from the medium” N. Menschutkin, 1890 г.

56. Medium = Environment Solvent Cages of various types Crystalline environment in molecular crystals