Guest Inclusion in Butadiyne -Bridged Macrocycles （ ブ タジイン 架橋マクロサイクルのゲスト分子 å

1. Guest Inclusion in Butadiyne-Bridged Macrocycles（ブタジイン架橋マクロサイクルのゲスト分子包摂） Tobe Lab. M1 Hiroshi Takeda

2. Contents • Host–Guest Chemistry • About Macrocycle • Complexationof Butadiyne-Bridged Pyridinophaneand TropyliumCation • STM & Guest Inclusion Ability • My Work • Summary

3. Contents • Host–Guest Chemistry • About Macrocycle • Complexationof Butadiyne-Bridged Pyridinophaneand TropyliumCation • STM & Guest Inclusion Ability • My Work • Summary

4. Host–Guest Chemistry Like the relation between “a key and a keyhole”, an enzyme reaction may show high selectivity. The molecules called host have spaces where they can selectively recognize a specific molecule.The molecules called guest are accepted in a host molecules.We create the substances which show new recog-nition ability, and study about their interaction . ＋ guest host

5. Contents • Host–Guest Chemistry • About Macrocycle • Complexationof Butadiyne-Bridged Pyridinophaneand TropyliumCation • STM & Guest Inclusion Ability • My Work • Summary

6. About Macrocycle macrocycle Butadiyne-bridged pyridinophane （　　　　　　　　　　　　） butadiyne pyridine

7. Mechanism of Complexation δ－ δ－ δ+ δ－ δ－ Ion Dipole Interaction The ion-dipole interaction refers to weak noncovalent bonds. It is due to interactions between ions and polar groups of molecules (or induced dipoles).

8. Titration of Pyridinophan H H R= 1 8

9. Titration of Pyridinophan Kis complex formation constant : 錯形成定数 H K chemical shift R=C8H17 1 Addition of guest 9 concentration Shift

10. Contents • Host–Guest Chemistry • About Macrocycle • Complexationof Butadiyne-Bridged Pyridinophaneand TropyliumCation • STM & Guest Inclusion Ability • My Work • Summary

11. Complexationof Butadiyne-Bridged Pyridinophane and ＴropyliumCation in Ｓolution tropylium ion R=C8H17 2 1 R=C8H17 To examine the binding ability of pyridinophanes1 and 2, we choose tropylium ion as a guest ⇒the cationsize is slightly larger than the cavity of 1 but it is too small to fit the cavity of 2.

12. Complexationof Butadiyne-Bridged Pyridinophaneand TropyliumCation in Solution > R=C8H17 R=C8H17 2 1 The nonlinear least-squares regression analysis gave K11(1:1) and K21(2:1) →For 1, K11 = 3×103 M-1 and K21 = 3×104M-1 For 2, K11 = 1×102M-1 and K21 = 4×102M-1 The larger binding constants of 1than those of 2 　→The size of the cavity of 1 which fits better than that of 2. Kis complex formation constant :錯形成定数

13. Contents • Host–Guest Chemistry • About Macrocycle • Complexationof Butadiyne-Bridged Pyridinophaneand TropyliumCation • STM & Guest Inclusion Ability • My Work • Summary

14. Scanning Tunneling Microscopy(STM) Until the former half of the 1980s,It was the dream for researchers to study a substance with an atomic level by using the atomic resolution microscope. Invention of ＳＴＭ (Scanning Tunneling Microscopy) A scanning tunneling microscope (STM) is an instrument for imaging surfaces at the atomic level. Its development in 1981 ear- nedits inventors, Gerd Binnig and Heinrich Rohrer (at IBM Zürich), the Nobel Prize in Physics in 1986. Binnig Rohrer

15. electron Tunneling current Scanning Tunneling Microscopy (STM) Tip Tunneling current Sample

16. Scanning Tunneling Microscope (STM) Ji (tunneling current) Ji = Aexp(-Bd) Largechange Ji : tunneling current A, B : constant d : distance d (distance) Smallchange Tip Sample

17. Self-Assembly of Butadiyne-Bridged Pyridinophane 1 R = COOC8H17

18. Guest Inclusion Ability of Butadiyne-Bridged Pyridinophaneon Solid Surfaces An empty macrocycle1 ＋ 1 R = COOC8H17 Thebrighter spots within the cavity of 1 are trapped tropyliumcations.

19. Guest Inclusion Ability ofButadiyne-Bridged Pyridinophane on Solid Surfaces 1 3 ＋ R = COOC8H17 R = COOC8H17 ・Squares filled with a bright spot are 1+ tropyliumcation complex ・Darker square features are 3 ・They appear randomly in the domains

20. Guest Inclusion Ability of Butadiyne-Bridged Pyridinophaneon Solid Surfaces 1 3 R = COOC8H17 R = COOC8H17 Only 1 formed the complex with tropyliumcation ! ・Squares filled with a bright spot are 1+ tropyliumcation complex ・Darker square features are 3 ・They appear randomly in the domains

21. Contents • Host–Guest Chemistry • About Macrocycle • Complexationof Butadiyne-Bridged Pyridinophaneand TropyliumCation • STM & Guest Inclusion Ability • My Work • Summary

22. Purpose of My Work ・Formation of two-dimensional (2D) molecular networks on the solid surface. ・guest inclusion ability ・Synthesis of butadiyne-bridged pyridino phane which possesses a larger cavity ・Evaluation of its guest inclusion ＋

23. Contents • Host–Guest Chemistry • About Macrocycle • Complexationof Butadiyne-Bridged Pyridinophaneand TropyliumCation • STM & Guest Inclusion Ability • My Work • Summary

24. Summary • The tetragonal butadiyne-bridged pyridinophaneand tropyliumcation form the complex in solution. • The binding constants of tetragonal butadiyne-bridged pyridinophane are larger than those of hexagonal. • The tetragonal butadiyne-bridged pyridinophanealso forms complex with tropyliumcationon solid surfaces. • A purpose of my work is to synthesize butadiyne-bridged pyridinophanewhich possesses a larger cavity and evaluate its guest inclusion.

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