Víctor Blanco, Marcos Chas, Dolores Abella, Carlos Peinador,* and José M. Quintela*

1. Molecular Catenation via Metal-Directed Self-Assembly andπ-Donor/π-Acceptor Interactions: Efficient One-Pot Synthesis, Characterization, and Crystal Structures of [3]Catenanes Based on Pd or Pt Dinuclear Metallocycles Víctor Blanco, Marcos Chas, Dolores Abella, Carlos Peinador,* and José M. Quintela* J. Am. Chem. Soc. 2007, 129, 13978-13986 Speaker: 黃仁鴻

2. Synthesis of [n]Catenanes • π-Donor/π-Acceptor complexes • Hydrogen bond interactions • Anion templation • Metal complexation

3. A Chemically-Switchable [2]Catenane c a b Figure 1. The [2]catenane 14+ and the translational isomers (2A4+ and 2B4+) of the [2]catenane 24+. Balzani, V.; Credi, A.; Langford, S. J.; Raymo, F. M.; Stoddart, J. F.;Venturi, M. J. Am. Chem. Soc. 2000, 122, 3542.

4. Amide-Based Interlocked Compounds Leigh, D. A.; Venturini, A.; Wilson, A. J.; Wong, J. K. Y.; Zerbetto, F. Chem.-Eur. J. 2004, 10, 4960.

5. Anion-Templated Assembly of a [2]Catenane Figure 2. Strategy for assembly of [2]-catenanes via anion templation. Sambrook, M.; Wisner, J. A.; Paul, R. L.; Cowley, A. R.; Szemes, F.; Beer,P. D. J. Am. Chem. Soc. 2004, 126, 15364.

6. Catenanes Built Around Octahedral Transition Metals Figure 3. Synthesis of a catenane using an octahedral metal atom and three bidentate chelates: construction principle. Chambron, J.-C.; Collin, J.-P.; Heitz, V.;Jouvenot, D.; Kern, J.-M.; Mobian, P.; Pomeranc, D.; Sauvage, J.-P. Eur. J. Org. Chem. 2004, 1627.

7. Synthesis of [n]Catenanes • π-Donor/π-Acceptor complexes • Hydrogen bond interactions • Anion templation • Metal complexation

8. Structures of Molecular Components Used in This Work

9. Dinuclear molecular squares 3a,b • Pseudorotaxanes • [3]-Catenanes (BPP34C10)2-(3a,b) • [3]-Catenanes (DB24C8)2-(3a,b) • [3]-Catenanes (DN38C10)2-(3a,b)

10. Synthesis of Dinuclear Molecular Squares 3a,b

11. 1H NMR Spectrum of 3a·4OTf·4PF6 a 8.99 ppm a 8H 8H 4H 8H 8H 8H 8H 8.91 ppm △

12. g f e d c b a i h 13C NMR Spectrum of 3a·4OTf·4PF6 DEPT-135 CH CH CH CH CH2 CH2 C C

13. g f e d c b a i h HSQC Spectrum of 3a·4OTf·4PF6 13C NMR Heteronuclear Single Quantum Coherence 1H-13C 1J h i 1H NMR a a

14. g f h e d c b a i i h g b i h g a COSY Spectrum of 3a·4OTf·4PF6 1H NMR COrrelation SpectroscopY 1H-1H 3J 1H NMR e f a b

15. g f g e d c b a i h a c a f HMBC Spectrum of 3a·4OTf·4PF6 13C NMR Heteronuclear Multiple Bond Coherence 1H-13C 1J, 2J, 3J 1H NMR b

16. g f e d c b a i h 1H & 13C NMR Spectra of 3a·4OTf·4PF6 a b e f g i h a b c Δδ=3.1 ppm Δδ=1.6 ppm 126.2 ppm 154.0 ppm e b a f Δδ=3.5 ppm h 144.9 ppm d c g

17. 1H NMR Spectra of 1·2PF6 and 2aat Different Concentrations 10 mM 5 mM 2.5 mM 0.5 mM 1·2PF6

18. Dinuclear molecular squares 3a,b • Pseudorotaxanes • [3]-Catenanes (BPP34C10)2-(3a,b) • [3]-Catenanes (DB24C8)2-(3a,b) • [3]-Catenanes (DN38C10)2-(3a,b)

19. Rotaxane http://www.catenane.net/home/rotcatintro.html http://en.wikipedia.org/wiki/Rotaxane

20. Crystal Structure of Pseudorotaxane Complex between 1·2PF6 and DB24C8 [H…O] distances [C-H…O] angle a 2.52 Å 149° b 2.26 Å 167° c 2.21 Å 167° d 2.37 Å 168°

21. 1H NMR Spectrum of DB24C8-1·2PF6 Pseudorotaxane g f Δδ=0.30 ppm Δδ=0.40 ppm

22. Dinuclear molecular squares 3a,b • Pseudorotaxanes • [3]-Catenanes (BPP34C10)2-(3a,b) • [3]-Catenanes (DB24C8)2-(3a,b) • [3]-Catenanes (DN38C10)2-(3a,b)

23. 3.83 Å Crystal Structure of The [3]Catenane (BPP3410)2-(3a)

24. Partial 1H NMR Spectra of Metallocycle 3a and (BPP34C10)2-(3a) a b Δδ= -0.7ppm e f Δδ= -0.3ppm Δδ= -0.7ppm Δδ= -0.1ppm Figure 2. Partial 1H NMR (CD3CN, 500 MHz) spectra of metallocycle 3a (top) and (BPP34C10)2-(3a) at 237 K (bottom).

25. Electrospray Ionization MassSpectrometry 987.0 Isotope% H1(100.0%) C12(98.9%) 13(1.1%) N14(99.6%) 15(0.4%) O16(99.8%) 18(0.2%) F 19(100.0%) P31(100.0%) Pt 192(0.8%) 194(32.9%) 195(33.8%) 196(25.3%) 198 (7.2%) 987.0 [(BPP34C10)2-(3b) - 3PF6]+3 Figure 4. Observed (top) and theoretical (bottom) isotopic distribution forthe fragment [(BPP34C10)2-(3b) - 3PF6]+3.

26. Dinuclear molecular squares 3a,b • Pseudorotaxanes • [3]-Catenanes (BPP34C10)2-(3a,b) • [3]-Catenanes (DB24C8)2-(3a,b) • [3]-Catenanes (DN38C10)2-(3a,b)

27. 1H NMR Spectra of (DB24C8)2-(3a) Figure 5. Partial 1H NMR (CD3CN, 298 K) spectra of (a) metallocycle 3a (5 mM), (b) 3a (5 mM) + DB24C8 (10 mM), and (c) 3a (5 mM) + DB24C8(20 mM).

28. Crystal Structure of [3]Catenane (DB24C8)2-(3a)

29. Reversible Catenation of (DB24C8)2-(3a) Figure 6. 1H NMR (CD3CN, 300 MHz, 298 K) spectra of (a) metallocycle 3a (5 mM), (b) solution (a) + DB24C8 (20 mM), (c) solution (b) + KPF6 (20 mM), (d) solution (c) + 18C6 (20 mM).

30. Dinuclear molecular squares 3a,b • Pseudorotaxanes • [3]-Catenanes (BPP34C10)2-(3a,b) • [3]-Catenanes (DB24C8)2-(3a,b) • [3]-Catenanes (DN38C10)2-(3a,b)

31. Crystal Structure of (DN38C10)2-(3a)

32. Crystal Structure of (DN38C10)2-(3b)

33. Conclusions • Ligand 1‧2PF6 threads through the cavity of DB24C8 to generate a [2]pseudorotaxane that is stabilized principally by hydrogen-bonding interactions. • The solid-state structure of catenane (DB24C8)2-(3a) revealed that the Pd(en) corners of metallocycle are capped with two additional polyether cyclophanes to form a supramolecular complex composed of eight components. • The catenation process of (DB24C8)2-(3a) can be switched off and on in a controllable manner by successive addition of KPF6 and 18-crown-6.

34. Conclusions(continued) • The reported catenanes are composed of a dinuclear molecular square bridged by ligand 1‧2PF6 interpenetrated by two polyether macrorings. • X-ray crystallography in combination with NMR studies showed that π-πstacking and [C-H…π] interactions in addition to [C-H…O]hydrogen bonds are the noncovalent forces that stabilize the [3]catenanes.

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